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Self-Aggregation in Supramolecular Systems
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Self-Aggregation in Supramolecular Systems

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Physical Chemistry".

Deadline for manuscript submissions: closed (31 October 2020) | Viewed by 15927

Special Issue Editors

Prof. Dr. Alessandro D'Urso

E-Mail Website
Guest Editor
Dipartimento di Scienze Chimiche, Università degli Studi di Catania, Viale A. Doria 6, 95125 Catania, Italy
Interests: supramolecular chemistry related to porphyrin self-assembly and chirality; design of chiroptical probes for biomolecules conformations
Special Issues, Collections and Topics in MDPI journals
Prof. Dr. Maria Elena Fragala

E-Mail Website
Guest Editor
Università degli Studi di Catania, Dipartimento di Scienze Chimiche, Viale A. Doria 6, 95125 Catania, Italy
Interests: material chemistry; porphyrins; supramolecular chemistry; inorganic chemistry

Special Issue Information

Dear Colleagues,

Self-organization is the driving force that led to the evolution of life, and supramolecular chemistry mimics reactions in natural systems (such as enzymatic reactions, assembling of multiprotein complexes, and other recognition reactions driven by noncovalent interactions) with the aim to exploit spontaneous organization to attain a reproducible bottom–up approach from molecular to supramolecular levels. Rationalization of the spontaneous self-assembly paradigm will offer tremendous potentialities to obtain a wide variety of complex systems, having specific functionality and properties.

The aim of the Special Issue “Self-Aggregation in Supramolecular Systems” is to explore the more recent chemical strategies to hierarchically manipulate the cooperative nature of weak interactions. Design and reproducible synthesis of molecular organization to supramolecular levels allows triggering structures and properties of supramolecular entities.

This Special Issue will collect interdisciplinary contributions focusing on the versatility and wide potentialities of self-assembled molecular nanosystems relevant for advancing new nanoscale functional materials having multiple applications in medicine, material chemistry, and biotechnology. Paper exploiting chiral building blocks to realize chiral supramolecular systems and highlighting the importance of supramolecular chirality in noncovalent self-assembled species will also be covered in this issue.

Prof. Dr. Alessandro D'Urso
Prof. Dr. Maria Elena Fragala
Guest Editors

Manuscript Submission Information

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Keywords

  • Noncovalent synthesis
  • Hierarchical processes
  • Supramolecular chemistry
  • Self-assembled species
  • Supramolecular materials
  • Supramolecular chirality
  • Biomimetic systems
  • Functional nanostructures
  • Macrocycle chemistry

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Published Papers (5 papers)

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Research

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13 pages, 3210 KiB  
Article
Self-Assembly of Chiral Cyclohexanohemicucurbit[n]urils with Bis(Zn Porphyrin): Size, Shape, and Time-Dependent Binding
by Marko Šakarašvili, Lukas Ustrnul, Elina Suut, Jagadeesh Varma Nallaparaju, Kamini A. Mishra, Nele Konrad, Jasper Adamson, Victor Borovkov and Riina Aav
Molecules 2022, 27(3), 937; https://doi.org/10.3390/molecules27030937 - 29 Jan 2022
Cited by 1 | Viewed by 2770
Abstract
In order to investigate the ability of bis(zinc octaethylporphyrin) (bis–ZnOEP) to discriminate cyclohexanohemicucurbit[n]urils (cycHC[n]) of different shapes and sizes, the self-assembly of barrel-shaped chiral cycHC[n] with bis–ZnOEP was studied by various spectroscopic methods (absorption, fluorescence, [...] Read more.
In order to investigate the ability of bis(zinc octaethylporphyrin) (bis–ZnOEP) to discriminate cyclohexanohemicucurbit[n]urils (cycHC[n]) of different shapes and sizes, the self-assembly of barrel-shaped chiral cycHC[n] with bis–ZnOEP was studied by various spectroscopic methods (absorption, fluorescence, circular dichroism (CD), and NMR). While the binding of 6-membered cycHC[6] induced a tweezer-like conformation followed by the formation of anti-form of bis–ZnOEP upon further addition of cycHC[6], the interaction of 8-membered cycHC[8] is more complex and proceeds through the featured syn-to-anti conformational change of bis–ZnOEP and further intermolecular self-assembly via multiple noncovalent associations between cycHC[8] and bis–ZnOEP. Whilst bis–porphyrins are known to be effective chemical sensors able to differentiate various guests based on their chirality via induced CD, their ability to sense small differences in the shape and size of relatively large macrocycles, such as chiral cycHC[6] and cycHC[8], is scarcely examined. Both studied complexes exhibited characteristic induced CD signals in the region of porphyrin absorption upon complexation. Full article
(This article belongs to the Special Issue Self-Aggregation in Supramolecular Systems)
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12 pages, 2686 KiB  
Article
Kinetic Investigation on Tetrakis(4-Sulfonatophenyl)Porphyrin J-Aggregates Formation Catalyzed by Cationic Metallo-Porphyrins
by Ilaria Giuseppina Occhiuto, Roberto Zagami, Mariachiara Trapani, Maria Angela Castriciano, Andrea Romeo and Luigi Monsù Scolaro
Molecules 2020, 25(23), 5742; https://doi.org/10.3390/molecules25235742 - 5 Dec 2020
Cited by 6 | Viewed by 1951
Abstract
Under mild acidic conditions, various metal derivatives of tetrakis(4-N-methylpyridinium)porphyrin (gold(III), AuT4; cobalt(III), CoT4; manganese(III), MnT4 and zinc(II), ZnT4) catalytically promote the supramolecular assembling process of the diacid 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (H2TPPS4) into [...] Read more.
Under mild acidic conditions, various metal derivatives of tetrakis(4-N-methylpyridinium)porphyrin (gold(III), AuT4; cobalt(III), CoT4; manganese(III), MnT4 and zinc(II), ZnT4) catalytically promote the supramolecular assembling process of the diacid 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (H2TPPS4) into J-aggregates. The aggregation kinetics have been treated according to a well-established model that involves the initial formation of a critical nucleus containing m porphyrin units, followed by autocatalytic growth, in which the rate evolves as a power of time. An analysis of the extinction time traces allows to obtain the rate constants for the auto-catalyzed pathway, kc, and the number of porphyrins involved in the initial seeding. The aggregation kinetics have been investigated at fixed H2TPPS4 concentration as a function of the added metal derivatives MT4. The derived rate constants, kc, obey a rate law that is first order in [MT4] and depend on the specific nature of the catalyst in the order AuT4 > CoT4 > MnT4 > ZnT4. Both resonance light scattering (RLS) intensity and extinction in the aggregated samples increase on increasing [MT4]. With the exception of AuT4, the final aggregated samples obtained at the highest catalyst concentration exhibit a negative Cotton effect in the J-band region, evidencing the occurrence of spontaneous symmetry breaking. The role of the nature of the metal derivative in terms of overall charge and presence of axial groups will be discussed. Full article
(This article belongs to the Special Issue Self-Aggregation in Supramolecular Systems)
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10 pages, 1806 KiB  
Communication
Supramolecular Sensing of a Chemical Warfare Agents Simulant by Functionalized Carbon Nanoparticles
by Nunzio Tuccitto, Luca Spitaleri, Giovanni Li Destri, Andrea Pappalardo, Antonino Gulino and Giuseppe Trusso Sfrazzetto
Molecules 2020, 25(23), 5731; https://doi.org/10.3390/molecules25235731 - 4 Dec 2020
Cited by 18 | Viewed by 3296
Abstract
Real-time sensing of chemical warfare agents by optical sensors is today a crucial target to prevent terroristic attacks by chemical weapons. Here the synthesis, characterization and detection properties of a new sensor, based on covalently functionalized carbon nanoparticles, are reported. This nanosensor exploits [...] Read more.
Real-time sensing of chemical warfare agents by optical sensors is today a crucial target to prevent terroristic attacks by chemical weapons. Here the synthesis, characterization and detection properties of a new sensor, based on covalently functionalized carbon nanoparticles, are reported. This nanosensor exploits noncovalent interactions, in particular hydrogen bonds, to detect DMMP, a simulant of nerve agents. The nanostructure of the sensor combined with the supramolecular sensing approach leads to high binding constant affinity, high selectivity and the possibility to reuse the sensor. Full article
(This article belongs to the Special Issue Self-Aggregation in Supramolecular Systems)
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18 pages, 20861 KiB  
Article
Stacks of Azobenzene Stars: Self-Assembly Scenario and Stabilising Forces Quantified in Computer Modelling
by Vladyslav Savchenko, Markus Koch, Aleksander S. Pavlov, Marina Saphiannikova and Olga Guskova
Molecules 2019, 24(23), 4387; https://doi.org/10.3390/molecules24234387 - 30 Nov 2019
Cited by 6 | Viewed by 4095
Abstract
In this paper, the columnar supramolecular aggregates of photosensitive star-shaped azobenzenes with benzene-1,3,5-tricarboxamide core and azobenzene arms are analyzed theoretically by applying a combination of computer simulation techniques. Without a light stimulus, the azobenzene arms adopt the trans-state and build one-dimensional columns of [...] Read more.
In this paper, the columnar supramolecular aggregates of photosensitive star-shaped azobenzenes with benzene-1,3,5-tricarboxamide core and azobenzene arms are analyzed theoretically by applying a combination of computer simulation techniques. Without a light stimulus, the azobenzene arms adopt the trans-state and build one-dimensional columns of stacked molecules during the first stage of the noncovalent association. These columnar aggregates represent the structural elements of more complex experimentally observed morphologies—fibers, spheres, gels, and others. Here, we determine the most favorable mutual orientations of the trans-stars in the stack in terms of (i) the π – π distance between the cores lengthwise the aggregate, (ii) the lateral displacements due to slippage and (iii) the rotation promoting the helical twist and chirality of the aggregate. To this end, we calculate the binding energy diagrams using density functional theory. The model predictions are further compared with available experimental data. The intermolecular forces responsible for the stability of the stacks in crystals are quantified using Hirshfeld surface analysis. Finally, to characterize the self-assembly mechanism of the stars in solution, we calculate the hydrogen bond lengths, the normalized dipole moments and the binding energies as functions of the columnar length. For this, molecular dynamics trajectories are analyzed. Finally, we conclude about the cooperative nature of the self-assembly of star-shaped azobenzenes with benzene-1,3,5-tricarboxamide core in aqueous solution. Full article
(This article belongs to the Special Issue Self-Aggregation in Supramolecular Systems)
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Review

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18 pages, 2766 KiB  
Review
The Self-Aggregation of Porphyrins with Multiple Chiral Centers in Organic/Aqueous Media: The Case of Sugar- and Steroid-Porphyrin Conjugates
by Manuela Stefanelli, Federica Mandoj, Gabriele Magna, Raffaella Lettieri, Mariano Venanzi, Roberto Paolesse and Donato Monti
Molecules 2020, 25(19), 4544; https://doi.org/10.3390/molecules25194544 - 4 Oct 2020
Cited by 14 | Viewed by 3040
Abstract
An overview of the solvent-driven aggregation of a series of chiral porphyrin derivatives studied by optical methods (UV/Vis, fluorescence, CD and RLS spectroscopies) is herein reported. The investigated porphyrins are characterized by the presence in the meso-positions of glycol-, steroidal- and glucosteroidal moieties, [...] Read more.
An overview of the solvent-driven aggregation of a series of chiral porphyrin derivatives studied by optical methods (UV/Vis, fluorescence, CD and RLS spectroscopies) is herein reported. The investigated porphyrins are characterized by the presence in the meso-positions of glycol-, steroidal- and glucosteroidal moieties, conferring amphiphilicity and solubility in aqueous media to the primarily hydrophobic porphyrin platform. Aggregation of the macrocycles is driven by a change in bulk solvent composition, forming architectures with supramolecular chirality, steered by the stereogenic centers on the porphyrin peripheral positions. The aggregation behavior and chiroptical properties of the final aggregated species strongly depend on the number and stereogenicity of the ancillary groups that dictate the mutual spatial arrangement of the porphyrin chromophores and their further organization in larger structures, usually detectable by different microscopies, such as AFM and SEM. Kinetic studies are fundamental to understand the aggregation mechanism, which is frequently found to be dependent on the substrate concentration. Additionally, Molecular Mechanics calculations can give insights into the intimate nature of the driving forces governing the self-assembly process. The critical use of these combined methods can shed light on the overall self-assembly process of chirally-functionalized macrocycles, with important implications on the development of chiral porphyrin-based materials. Full article
(This article belongs to the Special Issue Self-Aggregation in Supramolecular Systems)
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