Organic–inorganic (O–I) nanomaterials are versatile platforms for an incredible high number of applications, ranging from heterogeneous catalysis to molecular sensing, cell targeting, imaging, and ...cancer diagnosis and therapy, just to name a few. Much of their potential stems from the unique control of organic environments around inorganic sites within a single O–I nanomaterial, which allows for new properties that were inaccessible using purely organic or inorganic materials. Structural and mechanistic characterization plays a key role in understanding and rationally designing such hybrid nanoconstructs. Here, we introduce a general methodology to identify and classify local (supra)molecular environments in an archetypal class of O–I nanomaterials, i.e., self-assembled monolayer-protected gold nanoparticles (SAM-AuNPs). By using an atomistic machine-learning guided workflow based on the Smooth Overlap of Atomic Positions (SOAP) descriptor, we analyze a collection of chemically different SAM-AuNPs and detect and compare local environments in a way that is agnostic and automated, i.e., with no need of a priori information and minimal user intervention. In addition, the computational results coupled with experimental electron spin resonance measurements prove that is possible to have more than one local environment inside SAMs, being the thickness of the organic shell and solvation primary factors in the determining number and nature of multiple coexisting environments. These indications are extended to complex mixed hydrophilic–hydrophobic SAMs. This work demonstrates that it is possible to spot and compare local molecular environments in SAM-AuNPs exploiting atomistic machine-learning approaches, establishes ground rules to control them, and holds the potential for the rational design of O–I nanomaterials instructed from data.
Harnessing the reciprocal phobicity of hydrogenated and fluorinated thiolates proved to be a valuable strategy in preparing gold nanoparticles displaying mixed monolayers with a well-defined and ...pre-determined morphology. Our studies display that the organisation of the fluorinated ligands in phase-separated domains takes place even when these represent a small fraction of the ligands grafted on the gold surface. Using simple model ligands and by combining
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F NMR or ESR spectroscopies, and multiscale molecular simulations, we could demonstrate how the monolayer morphology responds in a predictable manner to structural differences between the thiolates. This enables a straightforward preparation of gold nanoparticles with monolayers displaying stripe-like, Janus, patchy, and random morphologies. Additionally, solubility properties may be tuned as function of the nature of the ligands and of the monolayer morphology obtaining gold nanoparticles soluble in organic solvents or in aqueous solutions. Most importantly, this rich diversity can be achieved not by resorting to ad hoc developed fabrication techniques, but rather relying on the spontaneous self-sorting of the ligands upon assembly on the nanoparticle surface. Besides enabling control over the monolayer morphology, fluorinated ligands endow the nanoparticles with several properties that can be exploited in the development of novel materials with applications, for instance in drug delivery and diagnostic imaging.
New ionophores based on a hydrophobic helical Aib-peptide show high activity on model membranes and an attracting antimicrobial activity against a broad spectrum of microorganisms. Display omitted
...Two new synthetic ionophores in which the hydrophobic portion is represented by a short helical Aib-peptide (Aib=α-amino-isobutyric acid) and the hydrophilic one is a poly-amino (1a) or a polyether (1b) chain have been prepared. The two conjugates show a high ionophoric activity in phospholipid membranes being able to efficiently dissipate a pH gradient and, in the case of 1b, to transport Na+ across the membrane. Bioactivity evaluation of the two conjugates shows that 1a has a moderate antimicrobial activity against a broad spectrum of microorganisms and it is able to permeabilize the inner and the outer membrane of Escherichia coli cells.
Low intrinsic toxicity, high solubility, and stability are important and necessary features of gold nanoparticles to be used in the biomedical field. In this context, charged nanoparticles proved to ...be very versatile, and among them charged mixed-monolayer gold nanoparticles, displaying monolayers with well-defined morphologies, represent a paradigm. By using mixtures of hydrogenated and fluorinated thiols, the formation of monolayer domains may be brought to an extreme because of the immiscibility of fluorinated and hydrogenated chains. Following this rationale, mixed monolayer gold nanoparticles featuring ammonium, sulfonate, or carboxylic groups on their surface were prepared by using amphiphilic hydrogenated thiols and 1H,1H,2H,2H-perfluoro-alkanethiols. The toxicity of these systems was assessed in HeLa cells and was found to be, in general, low even for the cationic nanoparticles which usually show a high cytotoxicity and is comparable to that of homoligand gold nanoparticles displaying amphiphiliccharge neutralhydrogenated or fluorinated thiolates in their monolayer. These properties make the mixed ligand monolayer gold nanoparticles an interesting new candidate for medical application.
Herein, we report a facile and flexible synthesis of porous and highly faceted platinum nanoparticles (NPs) performed in the liquid phase. The synthesis is performed by reduction of platinum ...2,4-pentantedionate in the presence of oleylamine and oleic acid in dibenzyl ether at 200 °C. The growth process was monitored by time-course transmission electron microscopy (TEM), revealing a peculiar progressive evolution that, in comparison with previous methodologies, is quite unusual. In fact, the morphology evolves first through nanocubes, nanostars, and dendrites to arrive at porous multifaceted NPs. This offers the possibility to selectively obtain materials with different degrees of complexity at a different time of reaction with one synthetic approach. Moreover, fine tuning of the reaction conditions was achieved by assessing, in dedicated experiments, the effects of temperature, surfactant concentration, and surfactant ratio, allowing control on NPs’ dispersity and shape reproducibility. The dimensionally monodispersed NPs have a mean diameter of 52 ± 2 nm and display small regular crystallites with uniform facets exposed on the surface as evinced by high-resolution-TEM analysis. The as-prepared multifaceted platinum NPs were tested for oxygen reduction and methanol oxidation reactions exhibiting improved catalytic activity with respect to conventional Pt-based nanomaterials.
Hydrogen-Bonded Helical Organic Nanotubes Pantoş, G. Dan; Pengo, Paolo; Sanders, Jeremy K. M.
Angewandte Chemie (International ed.),
01/2007, Volume:
46, Issue:
1-2
Journal Article
Peer reviewed
Twist your tubes: The self‐assembly of small organic molecules is an entirely new approach to the synthesis of nanotubular structures possessing helical chirality. Amino acid derivatives of ...naphthalenediimide form such assemblies both in solution and in the solid state. The chirality of the nanotubes is determined by the constituent amino acid but is independent of the nature of the side chains.
Mixtures of fluorinated and hydrogenated compounds display peculiar properties arising from their mutual phobicity and the same applies to semifluorinated species in which a reciprocal phobicity ...pattern exists within the same molecule. The interest in assemblies comprising these species stems from the ease in which self-sorting can take place, allowing the preparation of compartmentalised molecular aggregates with unique hydrophobic patterns or surface features. Most importantly, this is the result of molecular properties rather than specifically designed fabrication techniques. This brief overview describes some examples that are instrumental to present the features of fluorinated/hydrogenated supramolecular assemblies in which self-sorting of the dislike units takes place at different length scales. This review is focussed on flat assemblies such as self-assembled monolayers on gold surfaces, Langmuir Blodgett films and on three dimensional assemblies such as micelles, vesicles and nanoparticles.
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