A compound eye-like morphology formed through hexagonal array of hemispherical microparticles where an alkyl-fullerene derivative self-assembled at atmosphere-sealed air/water interface.

Self-assembly processes are widely used in nature to form hierarchically organized structures, prompting us to investigate such processes at the macroscopic scale. We report an unprecedented approach toward the self-assembly of alkyl-fullerene (C) derivatives into a hexagonal array of hemispherical microparticles akin to the morphology of a compound eye. The method includes casting solvated alkyl-Ccompound on an air/water interface followed by controlled evaporation of the solvent under atmosphere-sealed conditions.

Human Hemoglobin-Based Zinc-Air Battery in a Neutral Electrolyte.

The use of human hemoglobin (Hb) as a catalytic component of the air electrode in a primary zinc-air battery with a neutral electrolyte has been investigated. Three different electrode modifications, using the drop-casting method, with Hb and Nafion were first tested in a three-electrode cell, obtaining the best oxygen electroreduction (ORR) performance and long-term stability with a Hb plus Nafion (Hb-Nafion)-modified electrode. The latter Hb-Nafion-based air electrode provided a higher specific capacity and discharge time than the opposite order (Nafion-Hb).

Supramolecular Large Nanosheets Assembled at Air/Water Interfaces and in Solution from Amphiphilic Heptagon-Containing Nanographenes.

We report the synthesis of a new set of amphiphilic saddle-shaped heptagon-containing polycyclic aromatic hydrocarbons (PAHs) functionalized with tetraethylene glycol chains and their self-assembly into large two-dimensional (2D) polymers. An in-depth analysis of the self-assembly mechanism at the air/water interface has been carried out, and the proposed arrangement models are in good agreement with the molecular dynamics simulations. Quite remarkably, the number and disposition of the tetraethylene glycol chains significantly influence the disposition of the PAHs at the interface and conditionate their packing under pressure.

Surface energy transfer in hybrid halide perovskite/plasmonic Au nanoparticle composites.

The incorporation of plasmonic metal nanoparticles (NPs) into the multilayered architecture of perovskite solar cells (PSCs) has been a recurrent strategy to enhance the performance of photovoltaic devices from the early development of this technology. However, the specific photophysical interactions between the metal NPs and the hybrid halide perovskites are still not completely understood. Herein, we investigate the influence of Au NPs on the photoluminescence (PL) signal of a thin layer of the CHNHPbI hybrid perovskite.

Amphiphilic polymers for aggregation-induced emission at air/liquid interfaces.

Polymersomes and related self-assembled nanostructures displaying Aggregation-Induced Emission (AIE) are highly relevant for plenty of applications in imaging, biology and functional devices. Experimentally simple, scalable and universal strategies for on-demand self-assembly of polymers rendering well-defined nanostructures are highly desirable. A purposefully designed combination of amphiphilic block copolymers including tunable lengths of hydrophilic polyethylene glycol (PEG) and hydrophobic AIE polymer poly(tetraphenylethylene-trimethylenecarbonate) (P(TPE-TMC)) has been studied at the air/liquid interface.

Mechanochemically Synthetized PAN-Based Co-N-Doped Carbon Materials as Electrocatalyst for Oxygen Evolution Reaction.

We report a new class of polyacrylonitrile (PAN)-based Co-N-doped carbon materials that can act as suitable catalyst for oxygen evolution reactions (OER). Different Co loadings were mechanochemically added into post-consumed PAN fibers. Subsequently, the samples were treated at 300 °C under air (PAN-A) or nitrogen (PAN-N) atmosphere to promote simultaneously the CoO species and PAN cyclization.

Folding and self-assembly of short intrinsically disordered peptides and protein regions.

Proteins and peptide fragments are highly relevant building blocks in self-assembly for nanostructures with plenty of applications. Intrinsically disordered proteins (IDPs) and protein regions (IDRs) are defined by the absence of a well-defined secondary structure, yet IDPs/IDRs show a significant biological activity. Experimental techniques and computational modelling procedures for the characterization of IDPs/IDRs are discussed.

Antibacterial Effect of Chitosan-Gold Nanoparticles and Computational Modeling of the Interaction between Chitosan and a Lipid Bilayer Model.

Pathogenic bacteria have the ability to develop antibiotic resistance mechanisms. Their action consists mainly in the production of bacterial enzymes that inactivate antibiotics or the appearance of modifications that prevent the arrival of the drug at the target point or the alteration of the target point itself, becoming a growing problem for health systems. Chitosan-gold nanoparticles (Cs-AuNPs) have been shown as effective bactericidal materials avoiding damage to human cells.

Biomineralization at fluid interfaces.

Biomineralization is of paramount importance for life on Earth. The delicate balance of physicochemical interactions at the interface between organic and inorganic matter during all stages of biomineralization resembles an extremely high complexity. The coordination of this sophisticated biological machinery and physicochemical scenarios is certainly a wonderful show of nature.

Thermal and light irradiation effects on the electrocatalytic performance of hemoglobin modified CoO-g-CN nanomaterials for the oxygen evolution reaction.

The oxygen evolution reaction (OER) plays a key role in the water splitting process and a high energy conversion efficiency is essential for the definitive advance of hydrogen-based technologies. Unfortunately, the green and sustainable development of electrocatalysts for water oxidation is nowadays a real challenge. Herein, a successful mechanochemical method is proposed for the synthesis of a novel hemoglobin (Hb) modified CoO/g-CN composite nanomaterial.

Prediction of paclitaxel pharmacokinetic based on in vitro studies: Interaction with membrane models and human serum albumin.

Interactions of paclitaxel (PTX) with models mimicking biological interfaces (lipid membranes and serum albumin, HSA) were investigated to test the hypothesis that the set of in vitro assays proposed can be used to predict some aspects of drug pharmacokinetics (PK). PTX membrane partitioning was studied by derivative spectrophotometry; PTX effect on membrane biophysics was evaluated by dynamic light scattering, fluorescence anisotropy, atomic force microscopy and synchrotron small/wide-angle X-ray scattering; PTX distribution/molecular orientation in membranes was assessed by steady-state/time-resolved fluorescence and computer simulations. PTX binding to HSA was studied by fluorescence quenching, derivative spectrophotometry and dynamic/electrophoretic light scattering.

Bioconjugated Plasmonic Nanoparticles for Enhanced Skin Penetration.

Plasmonic nanoparticles (NPs) are one of the most promising and studied inorganic nanomaterials for different biomedical applications. Plasmonic NPs have excellent biocompatibility, long-term stability against physical and chemical degradation, relevant optical properties, well-known synthesis methods and tuneable surface functionalities. Herein, we review recently reported bioconjugated plasmonic NPs using different chemical approaches and loading cargoes (such as drugs, genes, and proteins) for enhancement of transdermal delivery across biological tissues.

Subtle chemical modification for enrichment of Fmoc-amino acid at a phospholipid interface.

Amino acids including the Fmoc group (9-fluorenylmethyloxycarbonyl) are bioinspired molecules that display intriguing features in self-assembly and biological applications. The influence of a delicate chemical modification between Fmoc-F and Fmoc-Y on the interaction with a phospholipid surface was analyzed. Langmuir monolayers of the 1,2-dimyristoyl--3-phosphate (DMPA) phospholipid were used to mimic the eukaryotic cell membrane.

Optimization of Amino Acid Sequence of Fmoc-Dipeptides for Interaction with Lipid Membranes.

Fmoc-dipeptides appear as highly relevant building blocks in smart hydrogels and nanovehicles for biological applications. The interactions of the Fmoc-dipeptides with the cell membrane determine the efficiency of the nanomaterials based on the Fmoc-dipeptides' internalization of nanovehicles for drug delivery. Here, we aim to understand the interplay of the interactions between the Fmoc-dipeptides and a phospholipid surface as a function of the amino acid sequence.

Boosting the electrochemical oxygen reduction activity of hemoglobin on fructose@graphene-oxide nanoplatforms.

A metal-free oxygen reduction reaction (ORR) electrocatalyst with outstanding performance was obtained through an easy and one-pot synthesis of hemoglobin functionalized fructose@graphene-oxide (GO) nanocomposites. The active pyridinic nitrogen sites of the highly unfolded proteins together with the excellent electronic properties of GO appears to be the main factors causing the improved electrocatalytic activity.

Mimicking the bioelectrocatalytic function of recombinant CotA laccase through electrostatically self-assembled bioconjugates.

Unprecedented 3D nanobiosystems composed of recombinant CotA laccases and citrate-stabilised gold nanoparticles have been successfully achieved by an electrostatic self-assembly strategy. The bioelectrochemical reduction of O2 driven by CotA laccase at the spore coat was mimicked. Consequently key insights into its bioelectrocatalytic function were unravelled.

Folding of cytosine-based nucleolipid monolayer by guanine recognition at the air-water interface.

Monolayers of a cytosine-based nucleolipid (1,2-dipalmitoyl-sn-glycero-3-(cytidine diphosphate) (ammonium salt), CDP-DG) at basic subphase have been prepared at the air-water interface both in absence and presence of guanine. The formation of the complementary base pairing is demonstrated by combining surface experimental techniques, i.e.

Unravelling the 2D self-assembly of Fmoc-dipeptides at fluid interfaces.

Dipeptides self-assemble into supramolecular structures showing plenty of applications in the nanotechnology and biomedical fields. A set of Fmoc-dipeptides with different aminoacid sequences has been synthesized and their self-assembly at fluid interfaces has been assessed. The relevant molecular parameters for achieving an efficient 2D self-assembly process have been established.

Fluorinated CdSe/ZnS quantum dots: Interactions with cell membrane.

Fluorescent inorganic quantum dots are highly promising for biomedical applications as sensing and imaging agents. However, the low internalization of the quantum dots, as well as for most of the nanoparticles, by living cells is a critical issue which should be solved for success in translational research. In order to increase the internalization rate of inorganic CdSe/ZnS quantum dots, they were functionalized with a fluorinated organic ligand.

Surface-Active Fluorinated Quantum Dots for Enhanced Cellular Uptake.

Fluorescent nanoparticles, such as quantum dots, hold great potential for biomedical applications, mainly sensing and bioimaging. However, the inefficient cell uptake of some nanoparticles hampers their application in clinical practice. Here, the effect of the modification of the quantum dot surface with fluorinated ligands to increase their surface activity and, thus, enhance their cellular uptake was explored.

Organization and structure of mixed Langmuir films composed of polydiacetylene and hemicyanine.

Mixed Langmuir monolayers of 10,12-Pentacosadiynoic acid (DA) monomer and an amphiphilic Hemicyanine dye derivative have been formed at the air/water interface. Two derivatives of docosylpyridinium have been used, with either one included in the monolayer in 1:1molar ratio. The DA monomers within the mixed monolayers have been polymerized in situ at the air/water interface.

Mechanosensitive Gold Colloidal Membranes Mediated by Supramolecular Interfacial Self-Assembly.

The ability to respond toward mechanical stimuli is a fundamental property of biological organisms at both the macroscopic and cellular levels, yet it has been considerably less observed in artificial supramolecular and colloidal homologues. An archetypal example in this regard is cellular mechanosensation, a process by which mechanical forces applied on the cell membrane are converted into biochemical or electrical signals through nanometer-scale changes in molecular conformations. In this article, we report an artificial gold nanoparticle (Au NP)-discrete π-conjugated molecule hybrid system that mimics the mechanical behavior of biological membranes and is able to self-assemble into colloidal gold nanoclusters or membranes in a controlled and reversible fashion by changing the concentration or the mechanical force (pressure) applied.

Directed self-assembly of inorganic nanoparticles at air/liquid interfaces.

Inorganic nanoparticles (NPs) appear as the forefront functional structure in nanotechnology. The preparation of functional materials based on inorganic NPs requires their assembly onto well-defined structures. Within this context, self-assembly at air-liquid interfaces is probably the best candidate for a universal procedure for active materials composed of assembled NPs.

Interfacial Activity of Gold Nanoparticles Coated with a Polymeric Patchy Shell and the Role of Spreading Agents.

Gold patchy nanoparticles (PPs) were prepared under surfactant-free conditions by functionalization with a binary ligand mixture of polystyrene and poly(ethylene glycol) (PEG) as hydrophobic and hydrophilic ligands, respectively. The interfacial activity of PPs was compared to that of homogeneous hydrophilic nanoparticles (HPs), fully functionalized with PEG, by means of pendant drop tensiometry at water/air and water/decane interfaces. We compared interfacial activities in three different spreading agents: water, water/chloroform, and pure chloroform.

Janus gold nanoparticles obtained via spontaneous binary polymer shell segregation.

Janus gold nanoparticles are of high interest because they allow directed self-assembly and display plasmonic properties. We succeeded in coating gold nanoparticles with two different polymers that form a Janus shell. The spontaneous segregation of two immiscible polymers at the surface of the nanoparticles was verified by NOESY NMR and most importantly by electron microscopy analysis in two and three dimensions.