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A special issue of International Journal of Molecular Sciences (ISSN 1422-0067). This special issue belongs to the section "Materials Science".

Deadline for manuscript submissions: closed (31 October 2021) | Viewed by 29254

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Dr. John G. Hardy

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1. Department of Chemistry, Faraday Building, Lancaster University, Lancaster LA1 4YB, UK
2. Materials Science Institute, Faraday Building, Lancaster University, Lancaster LA1 4YB, UK
Interests: polymer synthesis; supramolecular materials; biomaterials; stimuli-responsive materials; drug delivery; tissue engineering; sustainability
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Dr. Emily R. Draper

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School of Chemistry, University of Glasgow, Glasgow G12 8QQ, UK
Interests: supramolecular; organic electronics; self-assembly; electrochromic; SANS; rheology; gels
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Dear Colleagues,

Nature employs a combination of supramolecular interactions (e.g., electrostatic, hydrophobic, π–π, cation/anion–π, van der Waals forces, hydrogen-bonding and metal coordination) to generate hierarchically ordered structures with remarkable stimuli-responsive properties. The same structure-directing forces can, in principle, be employed for the realization of manufactured assemblies with similar or perhaps even greater utility. In this Special Issue of the International Journal of Molecular Sciences devoted to "Supramolecular Materials", we warmly invite submissions related to the synthesis, characterization and technical/biomedical applications of supramolecular entities.

You may choose our Joint Special Issue in Chemistry.

Dr. John G. Hardy
Dr. Emily R. Draper
Guest Editors

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Keywords

supramolecular interactions
self-assembly
host-guest systems
template effects
dynamic covalent chemistry
supramolecular polymers
supracolloidal chemistry
supramolecular materials
supramolecular optoelectronics
supramolecular theranostics

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Supramolecular Materials in Chemistry (1 article)

Published Papers (9 papers)

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23 pages, 39007 KiB

Open AccessArticle

Two-Dimensional Titanium Dioxide–Surfactant Photoactive Supramolecular Networks: Synthesis, Properties, and Applications for the Conversion of Light Energy

by Harold Lozano, Sindy Devis, Juan Aliaga, Matías Alegría, Hernán Guzmán, Roberto Villarroel, Eglantina Benavente and Guillermo González

Int. J. Mol. Sci. 2022, 23(7), 4006; https://doi.org/10.3390/ijms23074006 - 4 Apr 2022

Cited by 5 | Viewed by 2636

Abstract

The desire to harness solar energy to address current global environmental problems led us to investigate two-dimensional (2D) core–shell hybrid photocatalysts in the form of a 2D-TiO₂–surfactant, mainly composed of fatty acids. The bulk products, prepared by two slightly different methods, consist of stacked host–guest hybrid sheets held together by van der Waals forces between alkyl carboxylate moieties, favoring the synergistic conjugation of the photophysical properties of the core and the hydrophobicity of the self-assembled surfactant monolayer of the shell. X-ray diffraction and the vibrational characteristics of the products revealed the influence of synthesis strategies on two types of supramolecular aggregates that differ in the core chemical structure, guest conformers of alkyl surfactant tails and type, and the bilayer and monolayer of the structure of nanocomposites. The singular ability of the TiO₂ core to anchor carboxylate leads to commensurate hybrids, in contrast to both layered clay and layered double-hydroxide-based ion exchangers which have been previously reported, making them potentially interesting for modeling the role of fatty acids and lipids in bio-systems. The optical properties and photocatalytic activity of the products, mainly in composites with smaller bandgap semiconductors, are qualitatively similar to those of nanostructured TiO₂ but improve their photoresponse due to bandgap shifts and the extreme aspect-ratio characteristics of two-dimensional TiO₂ confinement. These results could be seen as a proof-of-concept of the potential of these materials to create custom-designed 2D-TiO₂–surfactant supramolecular photocatalysts. Full article

(This article belongs to the Special Issue Supramolecular Materials)

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15 pages, 3171 KiB

Open AccessArticle

Comparing C2=O and C2=S Barbiturates: Different Hydrogen-Bonding Patterns of Thiobarbiturates in Solution and the Solid State

by Chenming Li, Philipp Hilgeroth, Nazmul Hasan, Dieter Ströhl, Jörg Kressler and Wolfgang H. Binder

Int. J. Mol. Sci. 2021, 22(23), 12679; https://doi.org/10.3390/ijms222312679 - 24 Nov 2021

Cited by 6 | Viewed by 2690

Abstract

Carbonyl-centered hydrogen bonds with various strength and geometries are often exploited in materials to embed dynamic and adaptive properties, with the use of thiocarbonyl groups as hydrogen-bonding acceptors remaining only scarcely investigated. We herein report a comparative study of C2=O and C2=S barbiturates in view of their differing hydrogen bonds, using the 5,5-disubstituted barbiturate B and the thiobarbiturate TB as model compounds. Owing to the different hydrogen-bonding strength and geometries of C2=O vs. C2=S, we postulate the formation of different hydrogen-bonding patterns in C2=S in comparison to the C2=O in conventional barbiturates. To study differences in their association in solution, we conducted concentration- and temperature-dependent NMR experiments to compare their association constants, Gibbs free energy of association ∆G_assn., and the coalescence behavior of the N-H‧‧‧S=C bonded assemblies. In Langmuir films, the introduction of C2=S suppressed 2D crystallization when comparing B and TB using Brewster angle microscopy, also revealing a significant deviation in morphology. When embedded into a hydrophobic polymer such as polyisobutylene, a largely different rheological behavior was observed for the barbiturate-bearing PB compared to the thiobarbiturate-bearing PTB polymers, indicative of a stronger hydrogen bonding in the thioanalogue PTB. We therefore prove that H-bonds, when affixed to a polymer, here the thiobarbiturate moieties in PTB, can reinforce the nonpolar PIB matrix even better, thus indicating the formation of stronger H-bonds among the thiobarbiturates in polymers in contrast to the effects observed in solution. Full article

(This article belongs to the Special Issue Supramolecular Materials)

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20 pages, 1877 KiB

Open AccessArticle

Adamantane-Substituted Purines and Their β-Cyclodextrin Complexes: Synthesis and Biological Activity

by Michal Rouchal, Jana Rudolfová, Vladimír Kryštof, Veronika Vojáčková, Richard Čmelík and Robert Vícha

Int. J. Mol. Sci. 2021, 22(23), 12675; https://doi.org/10.3390/ijms222312675 - 24 Nov 2021

Cited by 8 | Viewed by 2494

Abstract

Cyclin-dependent kinases (CDKs) play an important role in the cell-division cycle. Synthetic inhibitors of CDKs are based on 2,6,9-trisubstituted purines and are developed as potential anticancer drugs; however, they have low solubility in water. In this study, we proved that the pharmaco-chemical properties of purine-based inhibitors can be improved by appropriate substitution with the adamantane moiety. We prepared ten new purine derivatives with adamantane skeletons that were linked at position 6 using phenylene spacers of variable geometry and polarity. We demonstrated that the adamantane skeleton does not compromise the biological activity, and some of the new purines displayed even higher inhibition activity towards CDK2/cyclin E than the parental compounds. These findings were supported by a docking study, which showed an adamantane scaffold inside the binding pocket participating in the complex stabilisation with non-polar interactions. In addition, we demonstrated that β-cyclodextrin (CD) increases the drug’s solubility in water, although this is at the cost of reducing the biochemical and cellular effect. Most likely, the drug concentration, which is necessary for target engagement, was decreased by competitive drug binding within the complex with β-CD. Full article

(This article belongs to the Special Issue Supramolecular Materials)

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17 pages, 3876 KiB

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PAMAM-calix-dendrimers: Synthesis and Thiacalixarene Conformation Effect on DNA Binding

by Olga Mostovaya, Pavel Padnya, Igor Shiabiev, Timur Mukhametzyanov and Ivan Stoikov

Int. J. Mol. Sci. 2021, 22(21), 11901; https://doi.org/10.3390/ijms222111901 - 2 Nov 2021

Cited by 20 | Viewed by 3249

Abstract

A convenient method for the synthesis of the first generation PAMAM dendrimers based on the thiacalix[4]arene has been developed for the first time. Three new PAMAM-calix-dendrimers with the macrocyclic core in cone, partial cone, and 1,3-alternate conformations were obtained with high yields. The interaction of the obtained compounds with salmon sperm DNA resulted in the formation of the associates of the size up to 200 nm, as shown by the UV-Vis spectroscopy, DLS, and TEM. It was demonstrated by the CD method that the structure of the DNA did not undergo significant changes upon binding. The PAMAM-calix-dendrimer based on the macrocycle in cone conformation stabilized DNA and prevented its degradation. Full article

(This article belongs to the Special Issue Supramolecular Materials)

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20 pages, 3162 KiB

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Insight into Molecular Interactions of Two Methyl Benzoate Derivatives with Bovine Serum Albumin

by Karolina Baranowska, Michał Mońka, Piotr Bojarski and Marek Józefowicz

Int. J. Mol. Sci. 2021, 22(21), 11705; https://doi.org/10.3390/ijms222111705 - 28 Oct 2021

Cited by 7 | Viewed by 2076

Abstract

The nature and mechanisms of interaction between two selected methyl benzoate derivatives (methyl o-methoxy p-methylaminobenzoate–I and methyl o-hydroxy p-methylaminobenzoate–II) and model transport protein bovine serum albumin (BSA) was studied using steady-state and time-resolved spectroscopic techniques. In order to understand the role of Trp residue of BSA in the I-BSA and II-BSA interaction, the effect of free Trp amino acid on the both emission modes (LE–locally excited (I and II) and ESIPT–excited state intramolecular proton transfer (II)) was investigated as well. Experimental results show that the investigated interactions (with both BSA and Trp) are mostly conditioned by the ground and excited state complex formation processes. Both molecules form stable complexes with BSA and Trp (with 1:1 stoichiometry) in the ground and excited states. The binding constants were in the order of 10⁴ M⁻¹. The absorption- and fluorescence-titration experiments along with the time-resolved fluorescence measurements show that the binding of the I and II causes fluorescence quenching of BSA through the static mechanism, revealing a 1:1 interaction. The magnitude and the sign of the thermodynamic parameters, ΔH, ΔS, and ΔG, determined from van’t Hoff relationship, confirm the predominance of the hydrogen-bonding interactions for the binding phenomenon. To improve and complete knowledge of methyl benzoate derivative-protein interactions in relation to supramolecular solvation dynamics, the time-dependent fluorescence Stokes’ shifts, represented by the normalized spectral response function c(t), was studied. Our studies reveal that the solvation dynamics that occurs in subpicosecond time scale in neat solvents of different polarities is slowed down significantly when the organic molecule is transferred to BSA cavity. Full article

(This article belongs to the Special Issue Supramolecular Materials)

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28 pages, 6906 KiB

Open AccessArticle

Effect of Washing Treatment on the Textural Properties and Bioactivity of Silica/Chitosan/TCP Xerogels for Bone Regeneration

by Antonio Pérez-Moreno, María Virtudes Reyes-Peces, José Ignacio Vilches-Pérez, Rafael Fernández-Montesinos, Gonzalo Pinaglia-Tobaruela, Mercedes Salido, Nicolás de la Rosa-Fox and Manuel Piñero

Int. J. Mol. Sci. 2021, 22(15), 8321; https://doi.org/10.3390/ijms22158321 - 2 Aug 2021

Cited by 12 | Viewed by 2815

Abstract

Silica/biopolymer hydrogel-based materials constitute very attractive platforms for various emerging biomedical applications, particularly for bone repair. The incorporation of calcium phosphates in the hybrid network allows for designing implants with interesting biological properties. Here, we introduce a synthesis procedure for obtaining silica–chitosan (CS)–tricalcium phosphate (TCP) xerogels, with CS nominal content varying from 4 to 40 wt.% and 10 to 20 wt.% TCP. Samples were obtained using the sol-gel process assisted with ultrasound probe, and the influence of ethanol or water as washing solvents on surface area, micro- and mesopore volume, and average pore size were examined in order to optimize their textural properties. Three washing solutions with different soaking conditions were tested: 1 or 7 days in absolute ethanol and 30 days in distilled water, resulting in E1, E7, and W30 washing series, respectively. Soaked samples were eventually dried by evaporative drying at air ambient pressure, and the formation of interpenetrated hybrid structures was suggested by Fourier transformed infrared (FTIR) spectroscopy. In addition the impact that both washing solvent and TCP content have on the biodegradation, in vitro bioactivity and osteoconduction of xerogels were explored. It was found that calcium and phosphate-containing ethanol-washed xerogels presented in vitro release of calcium (2–12 mg/L) and silicon ions (~60–75 mg/L) after one week of soaking in phosphate-buffered saline (PBS), as revealed by inductive coupled plasma (ICP) spectroscopy analysis. However, only the release of silicon was detected for water-washed samples. Besides, all the samples exhibited in vitro bioactivity in simulated body fluid (SBF), as well as enhanced in vitro cell growth and also significant focal adhesion development and maturation. Full article

(This article belongs to the Special Issue Supramolecular Materials)

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15 pages, 2771 KiB

Open AccessArticle

Supramolecular Chromatographic Separation of C₆₀ and C₇₀ Fullerenes: Flash Column Chromatography vs. High Pressure Liquid Chromatography

by Subbareddy Mekapothula, A. D. Dinga Wonanke, Matthew A. Addicoat, David J. Boocock, John D. Wallis and Gareth W. V. Cave

Int. J. Mol. Sci. 2021, 22(11), 5726; https://doi.org/10.3390/ijms22115726 - 27 May 2021

Viewed by 5025

Abstract

A silica-bound C-butylpyrogallol[4]arene chromatographic stationary phase was prepared and characterised by thermogravimetric analysis, scanning electron microscopy, NMR and mass spectrometry. The chromatographic performance was investigated by using C₆₀ and C₇₀ fullerenes in reverse phase mode via flash column and high-pressure liquid chromatography (HPLC). The resulting new stationary phase was observed to demonstrate size-selective molecular recognition as postulated from our in-silico studies. The silica-bound C-butylpyrogallol[4]arene flash and HPLC stationary phases were able to separate a C₆₀- and C₇₀-fullerene mixture more effectively than an RP-C₁₈ stationary phase. The presence of toluene in the mobile phase plays a significant role in achieving symmetrical peaks in flash column chromatography. Full article

(This article belongs to the Special Issue Supramolecular Materials)

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21 pages, 8139 KiB

Open AccessArticle

One-Dimensional Organic–Inorganic Material (C₆H₉N₂)₂BiCl₅: From Synthesis to Structural, Spectroscopic, and Electronic Characterizations

by Hela Ferjani, Hammouda Chebbi and Mohammed Fettouhi

Int. J. Mol. Sci. 2021, 22(4), 2030; https://doi.org/10.3390/ijms22042030 - 18 Feb 2021

Cited by 9 | Viewed by 2266

Abstract

The new organic–inorganic compound (C₆H₉N₂)₂BiCl₅ (I) has been grown by the solvent evaporation method. The one-dimensional (1D) structure of the allylimidazolium chlorobismuthate (I) has been determined by single crystal X-ray diffraction. It crystallizes in the centrosymmetric space group C2/c and consists of 1-allylimidazolium cations and (1D) chains of the anion BiCl₅²⁻, built up of corner-sharing [BiCl₆³⁻] octahedra which are interconnected by means of hydrogen bonding contacts N/C–H⋯Cl. The intermolecular interactions were quantified using Hirshfeld surface analysis and the enrichment ratio established that the most important role in the stability of the crystal structure was provided by hydrogen bonding and H···H interactions. The highest value of E was calculated for the contact N⋯C (6.87) followed by C⋯C (2.85) and Bi⋯Cl (2.43). These contacts were favored and made the main contribution to the crystal packing. The vibrational modes were identified and assigned by infrared and Raman spectroscopy. The optical band gap (Eg = 3.26 eV) was calculated from the diffuse reflectance spectrum and showed that we can consider the material as a semiconductor. The density functional theory (DFT) has been used to determine the calculated gap, which was about 3.73 eV, and to explain the electronic structure of the title compound, its optical properties, and the stability of the organic part by the calculation of HOMO and LUMO energy and the Fukui indices. Full article

(This article belongs to the Special Issue Supramolecular Materials)

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15 pages, 5611 KiB

Open AccessArticle

Photo-Responsive Supramolecular Micelles for Controlled Drug Release and Improved Chemotherapy

by Fasih Bintang Ilhami, Kai-Chen Peng, Yi-Shiuan Chang, Yihalem Abebe Alemayehu, Hsieh-Chih Tsai, Juin-Yih Lai, Yu-Hsuan Chiao, Chen-Yu Kao and Chih-Chia Cheng

Int. J. Mol. Sci. 2021, 22(1), 154; https://doi.org/10.3390/ijms22010154 - 25 Dec 2020

Cited by 16 | Viewed by 4085

Abstract

Development of stimuli-responsive supramolecular micelles that enable high levels of well-controlled drug release in cancer cells remains a grand challenge. Here, we encapsulated the antitumor drug doxorubicin (DOX) and pro-photosensitizer 5-aminolevulinic acid (5-ALA) within adenine-functionalized supramolecular micelles (A-PPG), in order to achieve effective drug delivery combined with photo-chemotherapy. The resulting DOX/5-ALA-loaded micelles exhibited excellent light and pH-responsive behavior in aqueous solution and high drug-entrapment stability in serum-rich media. A short duration (1–2 min) of laser irradiation with visible light induced the dissociation of the DOX/5-ALA complexes within the micelles, which disrupted micellular stability and resulted in rapid, immediate release of the physically entrapped drug from the micelles. In addition, in vitro assays of cellular reactive oxygen species generation and cellular internalization confirmed the drug-loaded micelles exhibited significantly enhanced cellular uptake after visible light irradiation, and that the light-triggered disassembly of micellar structures rapidly increased the production of reactive oxygen species within the cells. Importantly, flow cytometric analysis demonstrated that laser irradiation of cancer cells incubated with DOX/5-ALA-loaded A-PPG micelles effectively induced apoptotic cell death via endocytosis. Thus, this newly developed supramolecular system may offer a potential route towards improving the efficacy of synergistic chemotherapeutic approaches for cancer. Full article

(This article belongs to the Special Issue Supramolecular Materials)

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