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Nanomaterials
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Supramolecular Nano-architectures
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Supramolecular Nano-architectures

A special issue of Nanomaterials (ISSN 2079-4991).

Deadline for manuscript submissions: closed (15 December 2018) | Viewed by 33360

Special Issue Editors

Dr. Andrés Guerrero-Martínez

E-Mail Website
Guest Editor
Departamento de Química Física, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040 Madrid, Spain
Interests: nanoplasmonics; colloid chemistry; supramolecular chemistry; spectroscopy
Special Issues, Collections and Topics in MDPI journals
Dr. Fabio Cucinotta

E-Mail Website
Guest Editor
School of Chemistry, Newcastle University, Newcastle, UK
Interests: supramolecular photochemistry; molecular opto-electronics; hybrid materials; artificial photosynthesis; light-emitting devices

Special Issue Information

Dear Colleagues,

From the second half of the last century, research on supramolecular chemistry has attracted growing interest from the worldwide academic community and has allowed the emergence of cross-disciplinary studies at the frontiers between chemistry, physics, and biology. The development of bottom-up molecular and supramolecular approaches to assemble nano-architectures from nano-sized objects has achieved a high level of sophistication. Using synthetic strategies, where all facets of chemistry are involved (organic, inorganic, solid-state, polymer, biological), complex systems with functionalities beyond the reach of single molecules have been devised and have risen to the stage where they find applications in technologically-important fields. Several nano-structured systems are already being used as innovative advanced materials or as precursors to novel organic–inorganic hybrids, providing promising applications in optics, electronics, mechanics, membranes, functional and protective coatings, catalysis, sensors and biology.

The purpose of this Special Issue is to stimulate the publication of high-quality research articles, as well as reviews, that seek to address recent achievements in the preparation, characterization and application of supramolecular-designed nano-architectures, and exciting new developments in related aspects of supramolecular science, including future prospects and technological challenges.

Dr. Andrés Guerrero-Martínez
Dr. Fabio Cucinotta
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Nanomaterials is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2900 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • synthetic supramolecular strategies
  • hierarchically structured nano-systems
  • organic and metal-organic nano-structured hydrogels
  • opto-electronic properties of photonic
  • nano-structures
  • plasmonic nano-structures
  • supramolecular design of energy conversion systems
  • magnetic nano-materials
  • biohybrid nano-structures and their applications

Published Papers (7 papers)

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Research

18 pages, 4969 KiB  
Article
Facile Strategy for the Synthesis of Gold@Silica Hybrid Nanoparticles with Controlled Porosity and Janus Morphology
by Marina Santana Vega, Andrés Guerrero Martínez and Fabio Cucinotta
Nanomaterials 2019, 9(3), 348; https://doi.org/10.3390/nano9030348 - 03 Mar 2019
Cited by 11 | Viewed by 5586
Abstract
Hybrid materials prepared by encapsulation of plasmonic nanoparticles in porous silica systems are of increasing interest due to their high chemical stability and applications in optics, catalysis and biological sensing. Particularly promising is the possibility of obtaining gold@silica nanoparticles (Au@SiO2 NPs) with [...] Read more.
Hybrid materials prepared by encapsulation of plasmonic nanoparticles in porous silica systems are of increasing interest due to their high chemical stability and applications in optics, catalysis and biological sensing. Particularly promising is the possibility of obtaining gold@silica nanoparticles (Au@SiO2 NPs) with Janus morphology, as the induced anisotropy can be further exploited to achieve selectivity and directionality in physical interactions and chemical reactivity. However, current methods to realise such systems rely on the use of complex procedures based on binary solvent mixtures and varying concentrations of precursors and reaction conditions, with reproducibility limited to specific Au@SiO2 NP types. Here, we report a simple one-pot protocol leading to controlled crystallinity, pore order, monodispersity, and position of gold nanoparticles (AuNPs) within mesoporous silica by the simple addition of a small amount of sodium silicate. Using a fully water-based strategy and constant content of synthetic precursors, cetyl trimethylammonium bromide (CTAB) and tetraethyl orthosilicate (TEOS), we prepared a series of four silica systems: (A) without added silicate, (B) with added silicate, (C) with AuNPs and without added silicate, and (D) with AuNPs and with added silicate. The obtained samples were characterised by transmission electron microscopy (TEM), small angle X-ray scattering (SAXS), and UV-visible spectroscopy, and kinetic studies were carried out by monitoring the growth of the silica samples at different stages of the reaction: 1, 10, 15, 30 and 120 min. The analysis shows that the addition of sodium silicate in system B induces slower MCM-41 nanoparticle (MCM-41 NP) growth, with consequent higher crystallinity and better-defined hexagonal columnar porosity than those in system A. When the synthesis was carried out in the presence of CTAB-capped AuNPs, two different outcomes were obtained: without added silicate, isotropic mesoporous silica with AuNPs located at the centre and radial pore order (C), whereas the addition of silicate produced Janus-type Au@SiO2 NPs (D) in the form of MCM-41 and AuNPs positioned at the silica–water interface. Our method was nicely reproducible with gold nanospheres of different sizes (10, 30, and 68 nm diameter) and gold nanorods (55 × 19 nm), proving to be the simplest and most versatile method to date for the realisation of Janus-type systems based on MCM-41-coated plasmonic nanoparticles. Full article
(This article belongs to the Special Issue Supramolecular Nano-architectures)
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13 pages, 2221 KiB  
Article
Supramolecular Modification of ABC Triblock Terpolymers in Confinement Assembly
by Giada Quintieri, Marco Saccone, Matthias Spengler, Michael Giese and André H. Gröschel
Nanomaterials 2018, 8(12), 1029; https://doi.org/10.3390/nano8121029 - 10 Dec 2018
Cited by 18 | Viewed by 4103
Abstract
The self-assembly of AB diblock copolymers in three-dimensional (3D) soft confinement of nanoemulsions has recently become an attractive bottom up route to prepare colloids with controlled inner morphologies. In that regard, ABC triblock terpolymers show a more complex morphological behavior and could thus [...] Read more.
The self-assembly of AB diblock copolymers in three-dimensional (3D) soft confinement of nanoemulsions has recently become an attractive bottom up route to prepare colloids with controlled inner morphologies. In that regard, ABC triblock terpolymers show a more complex morphological behavior and could thus give access to extensive libraries of multicompartment microparticles. However, knowledge about their self-assembly in confinement is very limited thus far. Here, we investigated the confinement assembly of polystyrene-block-poly(4-vinylpyridine)-block-poly(tert-butyl methacrylate) (PS-b-P4VP-b-PT or SVT) triblock terpolymers in nanoemulsion droplets. Depending on the block weight fractions, we found spherical microparticles with concentric lamella–sphere (ls) morphology, i.e., PS/PT lamella intercalated with P4VP spheres, or unusual conic microparticles with concentric lamella–cylinder (lc) morphology. We further described how these morphologies can be modified through supramolecular additives, such as hydrogen bond (HB) and halogen bond (XB) donors. We bound donors to the 4VP units and analyzed changes in the morphology depending on the binding strength and the length of the alkyl tail. The interaction with the weaker donors resulted in an increase in volume of the P4VP domains, which depends upon the molar fraction of the added donor. For donors with a high tendency of intermolecular packing, a visible change in the morphology was observed. This ultimately caused a shape change in the microparticle. Knowledge about how to control inner morphologies of multicompartment microparticles could lead to novel carbon supports for catalysis, nanoparticles with unprecedented topologies, and potentially, reversible shape changes by light actuation. Full article
(This article belongs to the Special Issue Supramolecular Nano-architectures)
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13 pages, 3027 KiB  
Article
Molecular Dynamics Study on the Reverse Osmosis Using Multilayer Porous Graphene Membranes
by Zhongqiang Zhang, Fujian Zhang, Zhen Liu, Guanggui Cheng, Xiaodong Wang and Jianning Ding
Nanomaterials 2018, 8(10), 805; https://doi.org/10.3390/nano8100805 - 09 Oct 2018
Cited by 11 | Viewed by 3831
Abstract
In this study, the reverse osmosis (RO) of a salt solution was investigated using a molecular dynamics method to explore the performance of a multilayer porous graphene membrane. The effects of the salt solution concentration, pressure, layer separation and pore offset on the [...] Read more.
In this study, the reverse osmosis (RO) of a salt solution was investigated using a molecular dynamics method to explore the performance of a multilayer porous graphene membrane. The effects of the salt solution concentration, pressure, layer separation and pore offset on the RO performance of the membrane were investigated and the influences of the number of layers and the gradient structure were determined. The results show that as the salt solution concentration increases, the energy barrier of the water molecules passing through the bilayer porous graphene membranes changes slightly, indicating that the effect of the water flux on the membrane can be ignored. The salt rejection performance of the membrane improves with an increase in the concentration of the salt solution. When the pressure is increased, the energy barrier decreases, the water flux increases and the salt rejection decreases. When the layer separation of the bilayer porous graphene membrane is the same as the equilibrium spacing of the graphene membrane, the energy barrier is the lowest and the membrane water flux is the largest. The energy barrier of the bilayer porous graphene membrane increases with increasing layer separation, resulting in a decrease in the water flux of the membrane. The salt rejection increases with increasing layer separation. The water flux of the membrane decreases as the energy barrier increases with increasing pore offset and the salt rejection increases. The energy barrier effect is more pronounced for a larger number of graphene layers and the water flux of the membrane decreases because it is more difficult for the water molecules to pass through the porous graphene membrane. However, the salt rejection performance improves with the increase in the number of layers. The gradient pore structure enhances the energy barrier effect of the water molecules permeating through the membrane and the water flux of the membrane decreases. The salt rejection performance is improved by the gradient pore structure. The research results provide theoretical guidance for research on the RO performance of porous graphene membranes and the design of porous graphene membranes. Full article
(This article belongs to the Special Issue Supramolecular Nano-architectures)
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14 pages, 3783 KiB  
Article
Cyclodextrin-Grafted TiO2 Nanoparticles: Synthesis, Complexation Capacity, and Dispersion in Polymeric Matrices
by Pablo Monreal-Pérez, José Ramón Isasi, Javier González-Benito, Dania Olmos and Gustavo González-Gaitano
Nanomaterials 2018, 8(9), 642; https://doi.org/10.3390/nano8090642 - 22 Aug 2018
Cited by 10 | Viewed by 3578
Abstract
The modification of the surface of titanium dioxide nanoparticles (TiO2 NPs) by the incorporation of cyclodextrins (CDs), cyclic oligosaccharides with a hydrophobic cavity, can largely improve the functionality of TiO2 by lodging molecules of interest in the CD to act directly [...] Read more.
The modification of the surface of titanium dioxide nanoparticles (TiO2 NPs) by the incorporation of cyclodextrins (CDs), cyclic oligosaccharides with a hydrophobic cavity, can largely improve the functionality of TiO2 by lodging molecules of interest in the CD to act directly on the surface of the nanoparticles or for further release. With this aim, we have synthesized βCD-modified nanoparticles (βCDTiO2 NPs) by a two-step reaction that involves the incorporation of a spacer and then the linking of the macrocycle, and characterized them by thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). The capacity of the functionalized structures to trap model compounds (Rhodamine and 1-naphthol) has been compared to that of bare TiO2 NPs by fluorescence and Ultraviolet-visible (UV-visible) spectroscopy. The presence of the CDs on the surface of the TiO2 avoids the photo-degradation of the guest, which is of interest in order to combine the photocatalytic activity of TiO2, one of its most interesting features for practical purposes, with the delivery of compounds susceptible of being photo-degraded. The βCDTiO2 NPs have been dispersed in polymeric matrices of frequently used polymers, polyethylene (LDPE) and polyethylene oxide (PEO), by cryogenic high energy ball milling to produce nanocomposites in the form of films. The surface modification of the nanoparticles favors the homogenization of the filler in the matrix, while the nanoparticles, either in bare or functionalized form, do not seem to alter the crystallization properties of the polymer at least up to a 5% (w/w) load of filler. Full article
(This article belongs to the Special Issue Supramolecular Nano-architectures)
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11 pages, 2306 KiB  
Article
Cucurbit[n]uril (n = 6, 7) Based Carbon-Gold Hybrids with Peroxidase-Like Activity
by Liangfeng Zhang, Yan Zeng, Simin Liu and Feng Liang
Nanomaterials 2018, 8(5), 273; https://doi.org/10.3390/nano8050273 - 24 Apr 2018
Cited by 62 | Viewed by 5072
Abstract
Despite the combination of molecular recognition and local electric field enhancement endowing cucurbit[n]uril-capped metallic nanoparticles, indicating great potential in a variety of areas, prior work has paid little attention to carbonizing cucurbit[n]uril on the surface of gold nanoparticles, which [...] Read more.
Despite the combination of molecular recognition and local electric field enhancement endowing cucurbit[n]uril-capped metallic nanoparticles, indicating great potential in a variety of areas, prior work has paid little attention to carbonizing cucurbit[n]uril on the surface of gold nanoparticles, which may propose new carbon-gold hybrid materials with interesting applications. In this work, we developed a simple and cost-effective method to prepare carbon-gold hybrids by carbonizing cucurbit[n]uril modified gold nanoparticles. The as-prepared cucurbit[n]uril based carbon and carbon-gold hybrid materials have shown to possess peroxidase-like activity. All cucurbit[n]uril based nanomaterials exhibited high catalytic activity over a pH range 2–6 and more tolerant to high temperature (up to 60 °C) when compared to natural horseradish peroxidase. Full article
(This article belongs to the Special Issue Supramolecular Nano-architectures)
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19 pages, 7291 KiB  
Article
Supramolecular Control over the Interparticle Distance in Gold Nanoparticle Arrays by Cyclodextrin Polyrotaxanes
by Joao Paulo Coelho, José Osío Barcina, Elena Junquera, Emilio Aicart, Gloria Tardajos, Sergio Gómez-Graña, Pablo Cruz-Gil, Cástor Salgado, Pablo Díaz-Núñez, Ovidio Peña-Rodríguez and Andrés Guerrero-Martínez
Nanomaterials 2018, 8(3), 168; https://doi.org/10.3390/nano8030168 - 16 Mar 2018
Cited by 8 | Viewed by 5818
Abstract
Amphiphilic nonionic ligands, synthesized with a fixed hydrophobic moiety formed by a thiolated alkyl chain and an aromatic ring, and with a hydrophilic tail composed of a variable number of oxyethylene units, were used to functionalize spherical gold nanoparticles (AuNPs) in water. Steady-state [...] Read more.
Amphiphilic nonionic ligands, synthesized with a fixed hydrophobic moiety formed by a thiolated alkyl chain and an aromatic ring, and with a hydrophilic tail composed of a variable number of oxyethylene units, were used to functionalize spherical gold nanoparticles (AuNPs) in water. Steady-state and time-resolved fluorescence measurements of the AuNPs in the presence of α-cyclodextrin (α-CD) revealed the formation of supramolecular complexes between the ligand and macrocycle at the surface of the nanocrystals. The addition of α-CD induced the formation of inclusion complexes with a high apparent binding constant that decreased with the increasing oxyethylene chain length. The formation of polyrotaxanes at the surface of AuNPs, in which many α-CDs are trapped as hosts on the long and linear ligands, was demonstrated by the formation of large and homogeneous arrays of self-assembled AuNPs with hexagonal close packing, where the interparticle distance increased with the length of the oxyethylene chain. The estimated number of α-CDs per polyrotaxane suggests a high rigidization of the ligand upon complexation, allowing for nearly perfect control of the interparticle distance in the arrays. This degree of supramolecular control was extended to arrays formed by AuNPs stabilized with polyethylene glycol and even to binary arrays. Electromagnetic simulations showed that the enhancement and distribution of the electric field can be finely controlled in these plasmonic arrays. Full article
(This article belongs to the Special Issue Supramolecular Nano-architectures)
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12 pages, 3339 KiB  
Article
A Rapid and Semi-Quantitative Gold Nanoparticles Based Strip Sensor for Polymyxin B Sulfate Residues
by Yue Li, Liqiang Liu, Shanshan Song, Hua Kuang and Chuanlai Xu
Nanomaterials 2018, 8(3), 144; https://doi.org/10.3390/nano8030144 - 05 Mar 2018
Cited by 36 | Viewed by 4736
Abstract
Increasing attention is now being directed to the utilization of polymyxin B (PMB) as a last-line treatment for life-threatening infections caused by multidrug resistant Gram-negative bacteria. Unfortunately, polymyxins resistance is also increasingly reported, leaving a serious threat to human health. Therefore, the establishment [...] Read more.
Increasing attention is now being directed to the utilization of polymyxin B (PMB) as a last-line treatment for life-threatening infections caused by multidrug resistant Gram-negative bacteria. Unfortunately, polymyxins resistance is also increasingly reported, leaving a serious threat to human health. Therefore, the establishment of rapid detection methods for PMB residues is highly essential to ensure public health. In this study, two monoclonal antibodies (mAb; 2A2 and 3C6) were obtained using PMB-bovine serum albumin as the immunogen and PMB-ovalbumin as the coating antigen, which were prepared with N-(γ-maleimidobutyryloxy) succinimide ester and glutaraldehyde as cross-linking agents, respectively. Through an indirect competitive enzyme-linked immunosorbent assay, resultant two mAbs were compared and the results indicated that 3C6 showed higher sensitivity with a half maximum inhibition concentration of 13.13 ng/mL. Based on 3C6, a gold nanoparticles (AuNPs)-based immunochromatographic test (ICT) strip was then established, the mechanism of which is that free PMB competes with the fixed coating antigen to combine with mAb labeled by AuNPs. Using ICT strip to detect milk and animal feed samples revealed the visible detection limits were 25 ng/mL and 500 μg/kg, respectively and the cutoff limits were 100 ng/mL and 1000 μg/kg, respectively. The ICT strip provides results within 15 min, facilitating rapid and semi-quantitative analysis of PMB residues in milk and animal feed. Full article
(This article belongs to the Special Issue Supramolecular Nano-architectures)
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