Search Results (292)

Polyoxometalate (POM)-type supramolecular materials have unique structures and hold immense potential for development in the fields of biomedicine, information storage, and electrocatalysis. In this study, (NH₄)₃ [AlMo₆O₂₄H₆]·7H₂O was employed as a polyacid anion template, pentacyclic imidazole molecules served as organic ligands, and the moderate-temperature hydrothermal and natural evaporation methods were used in combination for the design and synthesis of two octamolybdenum-oxo cluster (homopolyacids containing molybdenum-oxygen structures as the main small-molecular structures)-based organic–inorganic hybrid compounds, [(C₃N₂H₅)(C₃N₂H₄)][(β-Mo₈O₂₆H₂)]_0.5 (1) and {Zn(C₃N₂H₄)₄}{[(γ-Mo₈O₂₆)(C₃N₂H₄)₂]_0.5}·2H₂O (2). Structural and property characterization revealed that both compounds crystallized in the P-1 space group with relatively stable three-dimensional structures under the action of hydrogen bonding. Upon temperature stimulation, the [Zn(C₃N₂H₄)₄]²⁺ cation and water molecules in 2 exhibited obvious oscillations, leading to significant dielectric anomalies at approximately 250 and 260 K when dielectric testing was conducted under heating conditions. Full article

A single-molecule magnet (SMM) is a molecule that functions as a magnet. SMMs can be explored not only for emerging technology but also the fundamental science of their quantum nature, nanometer sizes, and their ease of engineering. This review encompasses the state-of-the-art experiments and theories developed so far for SMMs. We briefly explore their experimental synthesis and characterization. In the experimental synthesis, we cover ‘Click Chemistry’ and supramolecular chemistry. The main experimental characterizations comprise superconducting quantum interference devices, electron paramagnetic resonance, neutron scattering, and X-ray magnetic circular dichroism. The theoretical and computational works based on the density functional theory, the post-Hartree–Fock methods, and the theory of open quantum systems are discussed. Moreover, we exemplify the numerous promising research areas for SMMs by discussing quantum technologies. We envision a brilliant future for the fundamental research and emerging applications of SMMs. Full article

Cellulose is a sustainable biopolymer, being renewable and abundant, non-toxic, biodegradable, and easily functionalizable. However, the development of hydrogels for tissue engineering applications presents significant challenges that require interdisciplinary expertise, given the intricate and dynamic nature of the human body. This paper delves into current research focused on creating advanced cellulose-based hydrogels with tailored mechanical, biological, chemical, and surface properties. These hydrogels show promise in healing, regenerating, and even replacing human tissues and organs. The synthesis of these hydrogels employs a range of innovative techniques, including supramolecular chemistry, click chemistry, enzyme-induced crosslinking, ultrasound, photo radiation, high-energy ionizing radiation, 3D printing, and other emerging methods. In the realm of tissue engineering, various types of hydrogels are explored, such as stimuli-responsive, hybrid, injectable, bio-printed, electrospun, self-assembling, self-healing, drug-releasing, biodegradable, and interpenetrating network hydrogels. Moreover, these materials can be further enhanced by incorporating cell growth factors, biological molecules, or by loading them with cells or drugs. Looking ahead, future research aims to engineer and tailor hydrogels to meet specific needs. This includes exploring safer and more sustainable materials and synthesis techniques, identifying less invasive application methods, and translating these studies into practical applications. Full article

Three diaryliodonium dicyanoargentates(I), [MesIAr][Ag(CN)₂] (Ar = Ph 1, Mes 2, 4-MeC₆H₄ 3; Mes = 2,4,6-Me₃C₆H₂), were prepared by anion metathesis. The X-ray structural analyses for these crystals revealed C–I^III∙∙∙N≡C halogen bonds (abbreviated as XB) between I atoms of diaryliodonium cations and N atoms of cyano groups, which provide different supramolecular organization. The noncovalent nature of these interactions was studied by density functional theory (DFT) calculations and topological analysis of the electron density distribution in the framework of the quantum theory of atoms in molecules (QTAIM) at the PBE-D3/jorge-DZP-DKH level of theory both in gas phase and crystal models. The philicities of partners in these contacts were confirmed by electron localization function (ELF) projections, electron density/electrostatic potential (ED/ESP) profiles, and Hirshfeld surfaces analysis. An analysis of the available crystallographic data from the literature allows us to find other examples of σ-hole interactions including the dicyanoargentate(I) anion, and the C–X∙∙∙N≡C (X = Br, I, Te) bonding were also confirmed theoretically. Full article

Cosmetic formulations are complex mixtures of ingredients that must fulfill several requirements. One of the challenges of the cosmetic industry is to find natural alternatives to replace synthetic polymers, preserving desirable sensory characteristics. The aim of this work is to induce the formation of gels, by replacing synthetic polymers with a low-molecular-weight gelator (LMWG), a small molecule able to self-assemble and form supramolecular networks. The impact of low-molecular-weight gelators on the environment is reduced as they are highly biodegradable. Thus, the behavior of solutions containing Boc-L-Dopa(Bn)₂-OH, an LMWG, together with ten different anionic surfactants, was studied to understand if the LMWG may act as a rheological modifier by increasing the viscosity of the formulation or forming gels with these ingredients. An amphoteric surfactant, cocamidopropyl betaine (CAPB), often used to increase cleansing gentleness, was also added to the solutions to better mimic a cosmetic formulation. In most cases, the addition of the gelator at only a 1% w/v concentration induces the gelification or an increase in the viscosity of the solutions, thus showing that this molecule is also able to self-assemble in complex mixtures. Full article

Multifunctional coupled hybrid materials have extremely high potential for application in a variety of complex scenarios owing to advantages such as versatility and controllable properties. In this study, a novel functional material with electromagnetic coupling properties [Ni(NCS)₄(C₆H₁₃N₄)₂] (1) was obtained by naturally evaporating an aqueous solution of nickel chloride hexahydrate, hexamethylenetetramine (HMTA), and potassium thiocyanate as raw materials. Structure–property characterization revealed that 1 crystallized in the P2₁/n space group with a two-dimensional (2D) network structure formed by hydrogen-bonding interactions between neighboring nickel complexes. Calculations using the Gaussian program indicated that HMTA exhibited pronounced spatial molecular rotation. This induced obvious reversible dielectric cycling near 240 K, giving rise to semiconducting properties and an optical band gap of 3.35 eV. Molecular rotation caused changes in the 2D network structure, inducing short-range magnetic ordering in the temperature range of 2–50 K. This resulted in the formation of a potential ferromagnet and the presence of a distinct reversible redox peak in the −0.2–0.8 V potential range. Structure–property analyses showed that 1 is a supramolecular rotation-induced semiconducting multifunctional crystalline material with reversible electromagnetic coupling properties. Full article

A series of three 1,3-phenylene bis-oxamides 3a–c, structurally related to the GPR35 receptor-agonist drug lodoxamide, has been synthesized by reacting the 1,3-phenylene bis-oxalamates 2a and 2b with amines. The obtained compounds were characterized by ¹H and ¹³C NMR, and IR spectroscopy, they showed characteristic signals for the aromatic, N―H, and C=O groups. Molecular structure was determined using single-crystal X-ray diffraction. The supramolecular architecture is driven by N―H···O=C, N―H···N, C—H···π, and O=C···O=C interactions depicting a supramolecular helix (3a) and tapes (3b–c). Intermolecular interactions were studied using Hirshfeld surface analysis, where N―H∙∙∙X (X = N, O) hydrogen bonding represents 30.2% to the surface of 3a and 17.8–18.8% to the surface of 3b–c. The most energetic interactions involve the amide N—H∙∙∙O hydrogen bonding, contributing in the −113.9 to −97.0 kJ mol⁻¹ range to the crystal energy, being more dispersive than electrostatic in nature. The molecular docking study was performed to evaluate the binding ability of 3a–c compounds to the GPR35 receptor, showing a favorable binding in a similar way to lodoxamide. Full article

The crystallinity of cellulose substrates is a key factor in their processability, as well as an indication of their susceptibility to undergo sensitive reactions (such as enzymatic saccharification) with high yields. FT-IR and X-ray diffraction spectroscopy are useful, reliable, and easy-to-reach solid-state characterization methods for assessing the crystallinity of different cellulose substrates including wood and wood-based materials. Due to their specific methodology, they can be used to analyze not only starting materials and their final products but also intermediates. Data obtained by these methods substantiated the structural changes in cellulose substrates, as well as the alterations that occurred in their supramolecular architectures. The conversion of crystalline cellulose I into amorphous cellulose II during enzymatic saccharification, with or without pre-treatment (solubilization in ILs), was evidenced beyond any reasonable doubt by FT-IR and XRD experimental results. Enzyme hydrolysis rates of the ILs-treated cellulose substrates can be significantly increased, as evidenced by reducing sugar yields. Crystallinity index values for cellulose of different origins (initial, pre-treated with ILs, and hydrolyzed with enzyme, as well as cellulose submitted to one-pot procedure with ILs and enzyme) can be determined using FTIR and X-ray diffraction data and discussed for comparison purposes. The same solid-state characterization methods can be also successfully employed for investigation of surface changes, expressed as cellulose crystallinity, in wood samples before and after impregnation with natural-based products, as well as under biodegradation conditions in soil burial tests. Full article

Metal phenolic networks (MPNs) have attracted significant attention due to their environmentally benign nature, broad compatibility, and universal adhesive properties, making them highly effective for modifying adsorbent surfaces. These supramolecular complexes are formed through the coordination of metal ions with natural phenolic ligands, resulting in stable structures while retaining the active adsorption sites of the ligands, thereby enhancing the adsorption performance of unmodified substrates. Among various MPNs, metal ion gallic acid (GA) networks are particularly well-known for their exceptional stability, biological activity, and superior adsorption ability. This review offers a comprehensive examination of GA-based MPN adsorbents, focusing on their formation chemistry, characterization techniques, and applications. The coordination chemistry underlying the stability of GA–metal complexes is analyzed through equilibrium studies, which are critical for understanding the robustness of MPNs. The main analytical methods for assessing metal ligand interactions are discussed, along with additional characterization techniques for evaluating adsorbent properties. This review also explores various synthesis and performance enhancement strategies for GA-based MPN adsorbents, including stand-alone MPNs, MPN-mediated mesoporous materials, MPN-MOF composites, and MPN-coated substrates. By consolidating current advancements in MPN-based adsorbents and offering fundamental insights into their chemistry and characterization, this review serves as a valuable resource for researchers seeking to develop stable, functional metal-organic materials. It aims to drive innovation in sustainable and efficient adsorbent technologies for diverse environmental and industrial applications. Full article

Supramolecular chemistry, a relatively newly grown field, has emerged as a useful tool to fabricate novel smart materials with multiple uses. Adhesives find numerous uses, from heavy engineering to biomedical science. Adhesives are available in nature; inspired by them and their mechanism of adhesion, several supramolecular adhesives have been developed. In this review, supramolecular chemistry for the design and fabrication of novel adhesives is discussed. The discussion is divided into two segments. The first one deals with key supramolecular forces, and their implication is designing novel adhesives. In the second part, key applications of supramolecular adhesives have been discussed with suitable examples. This type of review casts light on the current advancements in the field along with the prospects of development. Full article

Agriculture faces numerous challenges: infectious diseases through phytopathogens and soil nutrient deficiencies hinder plant growth, reducing crop yields. Biopolymer nanocomposites offer promising solutions to these challenges. In this work, we synthesize and characterize novel bionanocomposites (ι-CG-Mn) of manganese (hydr)oxide nanoparticles (approx. 3 to 11 nm) embedded in the matrix of the natural polysaccharide ι-carrageenan (ι-CG). Using spectroscopic methods we verify the presence of the nanoparticles in the polymer matrix while leaving the polysaccharide structural characteristics unaffected. Elemental analysis determines the mass content of metal ions in the ι-CG-Mn to be approx. 1 wt%. Electron microscopy techniques show the supramolecular organization of the ι-CG-Mn and the homogeneous nanoparticle distribution in the polymer matrix, while thermal analysis reveals that the bionanocomposite maintains high thermal stability. Moreover, the co-incubation of the phytopathogen Clavibacter sepedonicus with ι-CG-Mn inhibits the pathogen growth by 67% compared to the control. Our bionanocomposites demonstrate (1) strong bactericidal activity and (2) potential as microfertilizers that stimulate agricultural plant growth through the dosage of metal ions. These properties arise from the bioactivity of the widely available, naturally sulfated polysaccharide biopolymer matrix, combined with the antimicrobial effects of manganese (hydr)oxide nanoparticles, which together enhance the efficacy of the biocomposite. The non-toxic, biocompatible, and biodegradable nature of this biopolymer satisfies the high environmental demands for future biotechnological and agricultural technologies. Full article

Coffee and cocoa agribusinesses generate large volumes of byproducts, including coffee husk, coffee pulp, parchment skin, silver skin, and cocoa bean shell. Despite the rich composition of these materials, studies on biomolecule extraction with green solvents are still scarce, and further research is needed. Extraction methods using alternative solvents to obtain biomolecules must be developed to enhance the byproducts’ value and align with biorefinery concepts. This article reviews the compositions of coffee and cocoa byproducts, their potential applications, and biomolecule extraction methods, focusing on alternative solvents. The extraction methods currently studied include microwave-assisted, ultrasound-assisted, pulsed electric field-assisted, supercritical fluid, and pressurized liquid extraction. At the same time, the alternative solvents encompass the biobased ones, supercritical fluids, supramolecular, ionic liquids, and eutectic solvents. Considering the biomolecule caffeine, using alternative solvents such as pressurized ethanol, supercritical carbon dioxide, ionic liquids, and supramolecular solvents resulted in extraction yields of 2.5 to 3.3, 4.7, 5.1, and 1.1 times higher than conventional solvents. Similarly, natural deep eutectic solvents led to a chlorogenic acid extraction yield 84 times higher than water. The results of this research provide a basis for the development of environmentally friendly and efficient biomolecule extraction methods, improving the utilization of agricultural waste. Full article

In this work, we describe the synthesis, crystal structures and magnetic properties of four air-stable mononuclear lanthanide(III) complexes with the N-(2,4,6-trimethylphenyl)oxamate (Htmpa) of formula: n-Bu₄N[Nd(Htmpa)₄(H₂O)]·4H₂O (1), n-Bu₄N[Gd(Htmpa)₄(H₂O)]·3DMSO·2H₂O (2), n-Bu₄N[Tb(Htmpa)₄(H₂O)]·3DMSO·1H₂O (3) and n-Bu₄N[Dy(Htmpa)₄(H₂O)]·3DMSO·2H₂O (4) (n-Bu₄N⁺ = n-tetrabutylammonium; DMSO = dimethylsulfoxide). Their crystal structures reveal the occurrence of calixarene-type monoanionic species containing all-cis-disposed Htmpa ligands and one water molecule coordinated with the respective Ln^III ion (Ln = Nd, Gd, Tb and Dy), featuring a nine-coordinated environment with muffin (MFF-9) (1) or spherical-capped square antiprism (CSAPR-9) (2–4) geometry. The major difference between their crystal structures is related to the nature of crystallization solvent molecules, either water (1) or both DMSO and water (2–4). The intermolecular hydrogen bonds among the self-complementary Htmpa ligands in all four compounds mediated a 2 D supramolecular network in the solid state. Direct-current (dc) magnetic properties for 1–4 show typical behavior for the ground state terms of the Ln^III ions [⁴I_9/2 (Nd); ⁸S_7/2(Gd), ⁷F₆ (Tb), ⁶H^15/2 (Dy)]. Alternating-current (ac) magnetic measurements reveal the presence of slow magnetic relaxation without the presence of a dc field only for 4. In contrast, field-induced slow magnetic relaxation behavior was found in complexes 1, 2 and 3. Full article

Three novel multicomponent crystals of trimethylglycine with 2-cyanoguanidine, guanidinium and aminoguanidinium chlorides are synthesized and structurally characterized. All three crystal packings are based on the supramolecular synthon formed by two N–H groups of the guanidine species and carboxylate group of trimethylglycine (graph set notation R²₂(8)). Its enthalpy is about 50 kJ/mol. The three-dimensional structure of crystals is stabilized by intermolecular interactions of various types. The energy of C–H∙∙∙X⁻ interactions, where X = O, Cl, reaches 16 kJ/mol due to the acidic nature of methyl hydrogens. The possible structure of the trimethylglycine–urea–2H₂O complex is discussed. Its theoretical metric and spectroscopic parameters are in reasonable agreement with the available literature data on the deep eutectic solvent trimethylglycine–urea. Full article

In this study, unconventional C—Hlg···H–C (Hlg = Cl, Br, and I) interactions involving sp, sp², and sp³ organic halides were investigated at the RI-MP2/aug-cc-pVQZ level of theory. Energy Decomposition Analyses (EDA) and Natural Bonding Orbital (NBO) studies showed that these intermolecular contacts are mainly supported by orbital and dispersion contributions, which counteracted the unfavorable/slightly favorable electrostatics due to the halogen–hydrogen σ-hole facing. In addition, the Bader’s Quantum Theory of Atoms in Molecules (QTAIM) and the Noncovalent Interaction plot (NCIplot) visual index methodologies were used to further characterize the interactions discussed herein. We expect that the results reported herein will be useful in the fields of supramolecular chemistry, crystal engineering, and rational drug design, where the fine tuning of noncovalent interactions is crucial to achieve molecular recognition or a specific solid-state architecture. Full article