Special Issue "Self-Assembly in Chemistry and Supramolecular Chemistry"

A special issue of Applied Sciences (ISSN 2076-3417). This special issue belongs to the section "Chemistry".

Deadline for manuscript submissions: 15 July 2021.

Special Issue Editors

Dr. Pietro Calandra
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Guest Editor
DSCTM, National Council of Research, Piazzale Aldo Moro, 7, 00185 Rome, Italy
Interests: self-intermolecular interactions; chemistry; physics; materials; literature; science popularization
Special Issues and Collections in MDPI journals
Dr. Mikolaj Pochylskj
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Guest Editor
Faculty of Physics, Adam Mickiewicz University, Wieniawskiego 1, 61-712 Poznań, Poland
Interests: correlation spectroscopy; light scattering; polarimetry; instrument development; complex liquids; supercooled liquids; glass transition
Dr. Szerb Elisabeta Ildyko
Website1 Website2
Guest Editor
“Coriolan Drăgulescu” Institute of Chemistry, Romanian Academy, Timisoara 300223, Romania
Interests: inorganic and coordination chemistry; liquid crystals; self-assembly; functional materials
Special Issues and Collections in MDPI journals
Dr. Domenico Lombardo
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Guest Editor
Consiglio Nazionale delle Ricerche, Istituto Processi Chimico-Fisici, (CNR–IPCF), 98158 Messina, Italy
Interests: structure and interactuion in nano-colloids (polymers and block copolymers; dendrimers; lipids; proteins); self-assembly in nanostructured (and hybrid) materials; interaction of nanoparticles with model bio-membranes and biomaterials
Special Issues and Collections in MDPI journals

Special Issue Information

Dear Colleagues,

Self-assembly in chemistry has recently gained increasing attention due to its consequences with regard to developing novel materials. From a scientific point of view, the composition, intermolecular interactions, and chemical stability are pivotal factors in determining the properties of self-assembled structures. From a technological point of view, they are involved in drug delivery, nanoparticle synthesis, liquid crystals, and in several other state-of-the-art applications. Interest is also focused on self-assembly triggered by external fields (electrorheology, magnetorheology) or factors/conditions (smart materials).

The main focus of this Special Issue will be to point out the recent research progress on self-assembly in chemistry and supra-molecular chemistry. Interest in nano- and meso-structures from both the theoretical and experimental point of view is necessary to form a common language and knowledge basis for the scientific community. This Special Issue will be an international platform to synergically present the results of the most exciting experimental and theoretical studies in this field. Research articles, with a special emphasis on results obtained in the last five years, are welcome, as well as review articles on emerging fields and commentaries. Potential topics include, but are not limited to:

  • Stabilizing agents
  • Reactive and compartmentalizing media for nanoparticle synthesis
  • Nanoparticles
  • Nanostructures
  • Liquid crystals
  • Liquid membranes
  • Novel applications in chemistry
  • Modeling and simulation of structure–properties
  • Supramolecular ordering
  • Drug and gene delivery
  • Computational structure optimisation
  • Smart materials
  • Ferrofluidics
  • Magnetorheology
  • Electrorheology
  • Amphiphiles
  • Complex systems

Dr. Pietro Calandra
Dr. Mikolaj Pochylskj
Dr. Elisabeta Ildyko Szerb
Dr. Domenico Lombardo
Guest Editors

Manuscript Submission Information

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Keywords

  • Self-assembly
  • Supramolecular chemistry
  • Surfactants
  • Liquid crystals
  • Drug delivery
  • Nanostructures

Published Papers (4 papers)

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Research

Open AccessFeature PaperArticle
Molecular Assembling in Mixtures of Hydrophilic 1-Butyl-1-Methylpyrrolidinium Dicyanamide Ionic Liquid and Water
Appl. Sci. 2020, 10(14), 4837; https://doi.org/10.3390/app10144837 - 14 Jul 2020
Abstract
The infrared absorbance spectrum of the ionic liquid 1-butyl-1-methylpyrrolidinium dicyanamide, mixed with water at two different concentrations, was measured between 160 and 300 K in the mid infrared range. Both mixtures do not crystallize on cooling; however, remarkably, the one with an ionic [...] Read more.
The infrared absorbance spectrum of the ionic liquid 1-butyl-1-methylpyrrolidinium dicyanamide, mixed with water at two different concentrations, was measured between 160 and 300 K in the mid infrared range. Both mixtures do not crystallize on cooling; however, remarkably, the one with an ionic liquid (IL):water composition of 1:3 displays a cold crystallization process on heating in a restricted temperature range between 240 and 250 K. A portion of the water participates to the cold crystallization. On the contrary, with an IL:water composition of 1:6.6 no crystallization takes place. Upon water addition the vibration frequencies of the anion and of some lines of the cation are blue shifted, while the absorption lines of water are red shifted. These facts are interpreted as the evidence of the occurrence of the hydrogen bonding of water, as the hydrogen bonding acceptor with respect to the anion (anion∙∙∙O-H bonds develop) and as hydrogen donor for the cation (C-H∙∙∙O bonds can form). Microscopic inhomogeneities in the samples and their evolution with temperature are discussed. Full article
(This article belongs to the Special Issue Self-Assembly in Chemistry and Supramolecular Chemistry)
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Open AccessFeature PaperArticle
Cu Nano-Roses Self-Assembly from Allium cepa, L., Pyrolysis by Green Synthesis of C Nanostructures
Appl. Sci. 2020, 10(11), 3819; https://doi.org/10.3390/app10113819 - 30 May 2020
Cited by 1
Abstract
Carbon nanostructures are achieved by bio-waste Allium cepa, L., (onion vulgaris) peels through pyrolysis at 900 °C. They contain dispersed elements derived by their bio-precursors, like Mg, Ca, S, Na, K, and Cu. Here, we report the self-assembly of new Cu flower-shaped [...] Read more.
Carbon nanostructures are achieved by bio-waste Allium cepa, L., (onion vulgaris) peels through pyrolysis at 900 °C. They contain dispersed elements derived by their bio-precursors, like Mg, Ca, S, Na, K, and Cu. Here, we report the self-assembly of new Cu flower-shaped nanostructures organized as nano-roses. Remarkably, the nano-roses show rolled-up petals of Cu0 with a high chemical stability in air, exhibiting an intrinsic pure Cu crystalline phase. This suggests the exceptional potentiality to synthesize Cu0 nanostructures with novel physical/chemical properties. The size, morphology, and chemical composition were obtained by a combination of high-resolution scanning electron microscopy, energy dispersive X-ray spectroscopy, energy dispersive X-ray diffraction, and Raman spectroscopy. Full article
(This article belongs to the Special Issue Self-Assembly in Chemistry and Supramolecular Chemistry)
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Open AccessArticle
Superhydrophobic Self-Assembled Silane Monolayers on Hierarchical 6082 Aluminum Alloy for Anti-Corrosion Applications
Appl. Sci. 2020, 10(8), 2656; https://doi.org/10.3390/app10082656 - 12 Apr 2020
Cited by 2
Abstract
In this work, a two-stage methodology to design super-hydrophobic surfaces was proposed. The first step consists of creating a rough nano/micro-structure and the second step consists of reducing the surface energy using octadecyltrimethoxysilane. The surface roughening was realized by three different short-term pretreatments: [...] Read more.
In this work, a two-stage methodology to design super-hydrophobic surfaces was proposed. The first step consists of creating a rough nano/micro-structure and the second step consists of reducing the surface energy using octadecyltrimethoxysilane. The surface roughening was realized by three different short-term pretreatments: (i) Boiling water, (ii) HNO3/HCl etching, or (iii) HF/HCl etching. Then, the surface energy was reduced by dip-coating in diluted solution of octadecyltrimethoxysilane to allow the formation of self-assembled silane monolayers on a 6082-T6 aluminum alloy surface. Super-hydrophobic aluminum surfaces were investigated by SEM-EDS, FTIR, profilometry, and contact and sliding angles measurements. The resulting surface morphologies by the three approaches were structured by a dual hierarchical nano/micro-roughness. The surface wettability varied with the applied roughening pretreatment. In particular, an extremely high water contact angle (around 180°) and low sliding angle (0°) were evidenced for the HF/HCl-etched silanized surface. The results of electrochemical tests demonstrate a remarkable enhancement of the aluminum alloy corrosion resistance through the proposed superhydrophobic surface modifications. Thus, the obtained results evidenced that the anti-wetting behavior of the aluminum surface can be optimized by coupling an appropriate roughening pretreatment with a self-assembled silane monolayer deposition (to reduce surface energy) for anticorrosion application. Full article
(This article belongs to the Special Issue Self-Assembly in Chemistry and Supramolecular Chemistry)
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Open AccessArticle
Polysaccharides-Reinforced Bitumens: Specificities and Universality of Rheological Behavior
Appl. Sci. 2019, 9(24), 5564; https://doi.org/10.3390/app9245564 - 17 Dec 2019
Cited by 8
Abstract
The rheological properties of bitumens can be modified by the addition of specific chemical additives. Taking into account the molecular complex aggregation pattern, we hypothesized that macromolecules characterized by long, flexible, and hydrophilic chains can establish soft bridges connecting the different polar aggregates [...] Read more.
The rheological properties of bitumens can be modified by the addition of specific chemical additives. Taking into account the molecular complex aggregation pattern, we hypothesized that macromolecules characterized by long, flexible, and hydrophilic chains can establish soft bridges connecting the different polar aggregates of asphaltenes, strengthening their overall hierarchical supra-structures, and consequently increasing rheological performance at higher temperatures. Here, we propose the use of low cost and high availability polysaccharides as chemical additives to improve the rheological characteristics of a bitumen and to strengthen its thermal resistance. Fourteen different low-cost and high-availability polysaccharides, (flours, gums, and extracts from vegetable products) have been tested. While alghae euchemae have proved to be the most effective additive, corn and 00 flours are the least effective. Attempts to explain their differences have been made considering their chemical interactions with the polar molecules of asphaltenes within the complex framework of their supramolecular hierarchical structures. Through Arrhenius analysis, a correlation between activation energy and preexponential factor has been found, which can be useful for practical purposes, together with an unexpected consistency with the behavior of simple liquids, despite the striking differences in structure. Furthermore, a qualitative model has been suggested. The added value of this work is the focus on polysaccharides constituting low-cost, high availability materials which are sometimes even found as waste in industrial processes, all factors which, together with the environmental issues connected with their use, can be considered for large-scale applications. Full article
(This article belongs to the Special Issue Self-Assembly in Chemistry and Supramolecular Chemistry)
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Planned Papers

The below list represents only planned manuscripts. Some of these manuscripts have not been received by the Editorial Office yet. Papers submitted to MDPI journals are subject to peer-review.

Title: Molecular assembling in mixtures of ionic liquids and water
Authors: O. Palumboa, F. Trequattrinib, J.-B. Brubachc, P. Royc, A. Paolonea
Affiliation: a Consiglio Nazionale delle Ricerche, Istituto dei Sistemi Complessi, UOS La Sapienza, Piazzale A. Moro 5, 00185 Roma, Italy ([email protected]) b Department of Physics, Sapienza University of Rome, Piazzale A. Moro 5, 00185 Roma, Italy c Synchrotron SOLEIL, 91192 Gif Sur Yvette, France
Abstract: The charming properties that have made ionic liquids so interesting lie in the possibility of tailoring them by means of a proper choice of either the cation or the anion or by mixing with other liquids, such as water, alcohols or different ILs [1]. A deep understanding of their microscopic properties and of the assembling of ions in mixed systems is fundamental in order to master such possibility. The combined use of vibrational spectroscopies measurements and ab-initio calculations is a powerful tool to obtain information about the microscopic configurations [1-3] and about the phase transitions and the kind of interactions occurring in the system, which determinate the structure and the properties of ILs. In this study we compare the effects of water on the phase diagram of the hydrophilic 1-butyl-1-methylpyrrolidinium dicyanamide ionic liquid from room temperature down to 140 K, with a special attention to the changes of the environment of water molecules and the interface between water and ionic liquid. Combined infrared spectroscopy and ab-initio calculations provide information about the phase transitions and the intermolecular changes occurring in the liquid. The temperature dependence of the mid-infrared spectrum in the temperature range between 140 and 330 K indicates that in the ionic liquid containing only a small quantity of water due to absorption from the atmosphere, a cold crystallization takes place on heating between ≈240 and ≈260 K, that is suppressed when water is intentionally added in a greater amount. The analysis of the O-H stretching bands indicates the existence of two different “liquid like” water environments. When cold crystallization takes places the water molecules, which seem less coordinated to the other H2O molecules and more related to the anions, appear to be part of the crystallized sample. In both cases, it seems that at microscopic level the sample is not homogeneous, but more likely it is composed of separated clusters or regions of bulk water confined in the ionic liquid. These effects strongly resemble and further corroborate those already observed in the hydrophilic 1-butyl-1-methylimidazolium dicyanamide ionic liquid.[3]

Title: Thermal investigations on innovative nanostructured systems by FTIR spectroscopy
Authors: M. T. Caccamo, S. Magazù
Affiliation: Department of Mathematical and Informatics Sciences, Physical Sciences and Earth Sciences, Messina University, Viale F. Stagno D’Alcontres 31, 98166 Messina, Italy
Abstract: The paper reports a study on concentrated trehalose aqueous solutions which are attracting a great interest both for the scientific point of view and for the practical applications. In particular, despite the extraordinary bioprotective and osmoregulative properties of trehalose are well empirically defined, the underlying molecular mechanisms remain cryptic. It is known that to understand such mechanisms determining the effectiveness of trehalose, it is critical to characterize the structural and dynamical properties of disaccharide water solutions. In this context, the combination of acoustic levitation and InfraRed (IR) spectroscopy techniques offers a method to check the dehydration process of the diluted trehalose mixtures as a function of time and of the high concentration range. The levitated samples are analyzed by means of IR spectroscopy and the spectral data are processed by wavelet cross-correlation analysis.

Title: A comparative study of absorption spectra and photoelectrochemical properties of hybrid-organic and donor-acceptor dyes as supramolecular sensitizers for dye-sensitized solar cells.
Authors: S. Gullacea,b, G. Calogeroa, A. Bartolottaa.
Affiliation: a CNR-IPCF, Istituto per i Processi Chimico-Fisici, via F. Stagno D’Alcontres 37, I-98158 Messina, Italy. b Università di Messina, Viale F. Stagno D’Alcontres 31, 98166 Messina, Italy
Abstract: Here we studied and compared the sensitizing properties of two different hybrid-organic dyes, for photovoltaic applications in Grätzel cells. The first studied is the compound called C106 (NaRu (4,4'-bis (5- (hexylthio) thiophen-2- yl) -2,2'-bipyridine) (4-carboxylic acid-4'-carboxylate-2,2'-bipyridine)(NCS)2), while the second one is called Y123 (3- {6- {4- [bis (2 ', 4'-dihexyloxybiphenyl- 4-yl) amino-] phenyl} -4,4-dihexyl-cyclopenta- [2,1-b: 3,4-b] dithiphene-2-yl} -2-cyanoacrylic acid), is an organic dye free from central metal with a high molar extinction coefficient (ɛ) which makes it particularly interesting to be used in thin films of TiO2. The analysis of the absorption spectra of the Y123 photoanode shows two absorption maxima one at 401 nm and the other 541nm which, and despite the highest molar extinction coefficient, it exhibits lower intensity values than those of photoanodes with C106. Nevertheless, the photoelectrochemical performances of the two dyes when their cells are compared, employing a black background, are similar. We found that only employing a white background for the cells in the case of the Y123 dye a substantial increase in current produced and efficiency (+ 113% and +101 respectively) is observed.)

Title: Superhydrophobic self-assembled silane monolayers on etched 6082 Aluminium alloy for anti-corrosion applications
Authors: A. Khaskoussia, L. Calabreseb, E. Proverbiob
Affiliation: a National Interuniversity Consortium of Materials Science and Technology, INSTM, Via Giuseppe Giusti 9, 50121 Firenze, Italy ([email protected]) b Department of Engineering, University of Messina, Contrada di Dio Sant’Agata, 98166 Messina, Italy
Abstract: Super-hydrophobicity is one of the highly required surface properties for several industrial applications for which specific surface properties are required (such as self-cleaning, antifreeze, anti-adhesion or anti-corrosion applications). In such a context, in the recent years different approaches have been proposed aimed at obtaining super-hydrophobic hierarchical surfaces inspired by nature. Thanks to the opportunity to limit significantly the surface interaction between the liquids and the metallic support, the super-hydrophobic surfaces represent potential effective approaches to enhance the corrosion resistance of materials usually sensitive to corrosion degradation. However, usually the proposed approaches require complex synthesis processes and production technologies that are not easily scalable. In this paper a two-stage approach to obtain super-hydrophobic surfaces inspired by nature was proposed: 1) surface texturing: by using three short-term treatment with i) boiling water, ii) HF/HCl etching or iii) concentrated HNO3/HCl solution 2) Self-assembled silane monolayers: a thin layer of octadecylsilane was applied by dip-coating of diluted sol-gel solution and following polymerization for 3 hours at 100 °C in an oven to complete the low surface energy polymer curing. EN AW-6082 T6 aluminium alloy was used as substrate for the sample preparation. The proposed sol-gel self-assembling approach of silane layer not significantly modified the hierarchical microstructure of the etched aluminium substrate. The surface morphology of all three approaches is structured by a peculiar dual hierarchical nano-/micro-roughness profile. Furthermore, the sessile drop tests evidenced that the water contact angles ranged from 160° to nearly 180°. High water contact angle, above 175°, was evidenced for HF/HCl etched silanized surface. The results evidenced that he hydrophobic behavior of the aluminum surface can designed coupling different etching treatment (tailoring a peculiar micro-nano roughness profile) with a self-assembled silane monolayer deposition (to reduce surface energy). These results are promising for further development to better assess the relationship among hierarchical morphology, super-hydrophobicity and anti-corrosion performances.

Title: Novel methods to prepare ionic liquids. Last five years
Authors: L. Maiuoloa, D. Lombardob, E. Szerbc, M. Pochylskid, P. Calandrae
Affiliation: a Università della Calabria, Cosenza, Italy b Consiglio Nazionale delle Ricerche, Istituto Processi Chimico-Fisici, (CNR–IPCF), 98158 Messina, Italy c“Coriolan Dragulescu” Institute of Chemistry, Timisoara, Romania d Faculty of Physics, Adam Mickiewicz University, Wieniawskiego 1, 61-712 Poznań, Poland e Consiglio Nazionale delle Ricerche - Istituto per lo Studio dei Sistemi Nanostrutturati, Rome, Italy
Abstract: Ionic liquid (ILs), also called liquid electrolytes, ionic melts, ionic fluids, fused salts, liquid salts, or ionic glasses, are salts in the liquid state at a some arbitrary temperature, usually close to room temperature. So, they are largely made of ions and short-living ion pairs. The variable combination of cation and ion has an high impact on polarity, hydrophilicity/hydrophobicity and chemical-physical properties of ionic liquids, including their melting points. From the structural point of view, they are low-vapor-pressure strongly interacting fluids with an order extending to medium range (ionic self-assembly) as a consequence of strong electrostatic interactions. This scenario is further enriched by hydrophobic, steric and π–π interactions conferring complex behaviour to such systems. From the applicative point of view these substances materials are used for many purposes, from separation/extraction to chemical synthesis, from electric battery applications to green chemistry, prevalently for their appealing possibility of recycling and reusing. Although the term "ionic liquid" in the general sense was used already in the '40s, only recently a steep increase in their use occurred, which has triggered much research efforts for their preparation. This work will review the recent trends (last 5 years) for ionic liquid preparation hoping it will be useful for research facing this exciting field.

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