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Two-dimensional (2D) materials have attracted tremendous interest ever since the isolation of atomically thin sheets of graphene in 2004 due to the specific and versatile properties of these materials. However, the increasing production and use of 2D materials necessitate a thorough evaluation of the potential impact on human health and the environment. Furthermore, harmonized test protocols are needed with which to assess the safety of 2D materials. The Graphene Flagship project (2013–2023), funded by the European Commission, addressed the identification of the possible hazard of graphene-based materials as well as emerging 2D materials including transition metal dichalcogenides, hexagonal boron nitride, and others. Additionally, so-called green chemistry approaches were explored to achieve the goal of a safe and sustainable production and use of this fascinating family of nanomaterials. The present review provides a compact survey of the findings and the lessons learned in the Graphene Flagship.

In recent years, the use of free-standing carbon nanotube (CNT) films for neural tissue engineering has attracted tremendous attention. CNT films show large surface area and high electrical conductivity that combined with flexibility and biocompatibility may promote neuron growth and differentiation while stimulating neural activity. In addition, adhesion, survival, and growth of neurons can be modulated through chemical modification of CNTs. Axonal and synaptic signaling can also be positively tuned by these materials. Here we describe the ability of free-standing CNT films to influence neuronal activity. We demonstrate that the degree of cross-linking between the CNTs has a strong impact on the electrical conductivity of the substrate, which, in turn, regulates neural circuit outputs.

The design of cost-effective and efficient electrocatalysts for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is pivotal for the molecular hydrogen (H2) production from electrochemical water splitting as a future energy source. Herein, we show that the hybridization between multiple HER- and OER-active components is effective for the design and realization of bifunctional electrocatalysts for universal water splitting, i.e., in both acidic and alkaline media. Our strategy relies on the production and characterization of MoSe2holey flake:Mo2C ball hybrids supported by single-walled carbon nanotube (SWCNT) electrocatalysts. Flakes of MoSe2are produced through hydrogen peroxide (H2O2)-aided liquid phase exfoliation (LPE), which promotes both the exfoliation of the materials and the formation of nanopores in the flakes viachemical etching. The amount of H2O2in the solvent used for the exfoliation process is optimized to obtain ideal high ratio between edge and basal sites ratio, i.e., high-number of electrocatalytic sites. The hybridization of MoSe2flakes with commercial ball-like shaped Mo2C crystals facilitates the Volmer reaction, which works in both acidic and alkaline media. In addition, the electrochemical coupling between SWCNTs (as support) and MoSe2:Mo2C hybrids synergistically enhances both HER- and OER-activity of the native components, reaching high η10in acidic and alkaline media (0.049 and 0.089 V for HER in 0.5 M H2SO4and 1 M KOH, respectively; 0.197 and 0.241 V for OER in 0.5 M H2SO4and 1 M KOH, respectively). The exploitation of the synergistic effects occurring between multicomponent electrocatalysts, coupled with the production of the electrocatalysts themselves through scalable and cost-effective solution-processed manufacturing techniques, is promising to scale-up the production of H2viaefficient water splitting for the future energy portfolio.

Interface engineering of organic–inorganic halide perovskite solar cells (PSCs) plays a pivotal role in achieving high power conversion efficiency (PCE). In fact, the perovskite photoactive layer needs to work synergistically with the other functional components of the cell, such as charge transporting/active buffer layers and electrodes. In this context, graphene and related two-dimensional materials (GRMs) are promising candidates to tune “on demand” the interface properties of PSCs. In this work, we fully exploit the potential of GRMs by controlling the optoelectronic properties of molybdenum disulfide (MoS2) and reduced graphene oxide (RGO) hybrids both as hole transport layer (HTL) and active buffer layer (ABL) in mesoscopic methylammonium lead iodide (CH3NH3PbI3) perovskite (MAPbI3)-based PSCs. We show that zero-dimensional MoS2quantum dots (MoS2QDs), derived by liquid phase exfoliated MoS2flakes, provide both hole-extraction and electron-blocking properties. In fact, on one hand, intrinsic n-type doping-induced intraband gap states effectively extract the holes through an electron injection mechanism. On the other hand, quantum confinement effects increase the optical band gap of MoS2(from 1.4 eV for the flakes to >3.2 eV for QDs), raising the minimum energy of its conduction band (from −4.3 eV for the flakes to −2.2 eV for QDs) above the one of the conduction band of MAPbI3(between −3.7 and −4 eV) and hindering electron collection. The van der Waals hybridization of MoS2QDs with functionalized reduced graphene oxide (f-RGO), obtained by chemical silanization-induced linkage between RGO and (3-mercaptopropyl)trimethoxysilane, is effective to homogenize the deposition of HTLs or ABLs onto the perovskite film, since the two-dimensional nature of RGO effectively plugs the pinholes of the MoS2QD films. Our “graphene interface engineering” (GIE) strategy based on van der Waals MoS2QD/graphene hybrids enables MAPbI3-based PSCs to achieve a PCE up to 20.12% (average PCE of 18.8%). The possibility to combine quantum and chemical effects into GIE, coupled with the recent success of graphene and GRMs as interfacial layer, represents a promising approach for the development of next-generation PSCs.

Graphene and its derivatives are heralded as “miracle” materials with manifold applications in different sectors of society from electronics to energy storage to medicine. The increasing exploitation of graphene-based materials (GBMs) necessitates a comprehensive evaluation of the potential impact of these materials on human health and the environment. Here, we discuss synthesis and characterization of GBMs as well as human and environmental hazard assessment of GBMs using in vitroand in vivomodel systems with the aim to understand the properties that underlie the biological effects of these materials; not all GBMs are alike, and it is essential that we disentangle the structure–activity relationships for this class of materials.

Hydrogelation, the self-assembly of molecules into soft, water-loaded networks, is one way to bridge the structural gap between single molecules and functional materials. The potential of hydrogels, such as those based on perylene bisimides, lies in their chemical, physical, optical, and electronic properties, which are governed by the supramolecular structure of the gel. However, the structural motifs and their precise role for long-range conductivity are yet to be explored. Here, we present a comprehensive structural picture of a perylene bisimide hydrogel, suggesting that its long-range conductivity is limited by charge transfer between electronic backbones. We reveal nanocrystalline ribbon-like structures as the electronic and structural backbone units between which charge transfer is mediated by polar solvent bridges. We exemplify this effect with sensing, where exposure to polar vapor enhances conductivity by 5 orders of magnitude, emphasizing the crucial role of the interplay between structural motif and surrounding medium for the rational design of devices based on nanocrystalline hydrogels.

Short peptide hydrogels are attractive biomaterials but typically suffer from limited mechanical properties. Inclusion of other nanomaterials can serve the dual purpose of hydrogel reinforcement and of conferring additional physicochemical properties (e.g., self-healing, conductivity), as long as they do not hamper peptide self-assembly. In particular, nanocarbons are ideal candidates, and their physicochemical properties have demonstrated great potential in nanocarbon-polymer gel biomaterials for tissue engineering or drug delivery. Recently, increasing interest in supramolecular hydrogels drove research also on their enhancement with nanocarbons. However, little is known on the effect of nanocarbon morphology on the self-assembly of short peptides, which are among the most popular hydrogel building blocks. In this work, three different oxidized nanocarbons (i.e., carbon nanotube or CNT as 1D material, graphene oxide sheet or GO as 2D material, and carbon nanohorn or CNH as 3D material) were evaluated for their effects on the self-assembly of the unprotected tripeptide Leu-DPhe-DPhe at physiological conditions. Supramolecular hydrogels were obtained in all cases, and viscoelastic properties were clearly affected by the nanocarbons, which increased stiffness and resistance to applied stress. Notably, self-healing behavior was observed only in the case of CNTs. Tripeptide–nanotube interaction was noted already in solution prior to self-assembly, with the tripeptide acting as a dispersing agent in phosphate buffer. Experimental and in silicoinvestigation of the interaction between peptide and CNTs suggests that the latter acts as nucleation templates for self-assembly and reassembly. Overall, we provide useful insights for the future design of composite biomaterials with acquired properties.

Hybrid diimidazolium-based ionogels were obtained by dispersing nitrogen-doped carbon nanodots (NCNDs) in ionic liquid (IL) solutions and by using dicationic organic salts as gelators. The properties of the NCND-ionogels were studied in terms of thermal stability, mechanical strength, morphology, rheological, and microscopic analyses. Insights into the formation of the hybrid soft material were attained from kinetics of sol–gel phase transition and from estimating the size of the aggregates, obtained from opacity and resonance light-scattering measurements. We demonstrate that, on one hand, NCNDs were able to favor the gel formation both in the presence of gelating and nongelating ILs. On the other hand, the gelatinous matrix retains and, in some cases, improves the properties of NCNDs. The NCND-ionogels showed the typical fluorescence emission of the carbon dots and a notable antiradical activity, with higher efficiency as compared to the single components. The presented hybrid materials hold great promise for topical applications in antioxidant fields.

The insertion of intentional impurities, commonly referred to as doping, into colloidal semiconductor quantum dots (QDs) is a powerful paradigm for tailoring their electronic, optical, and magnetic behaviors beyond what is obtained with size-control and heterostructuring motifs. Advancements in colloidal chemistry have led to nearly atomic precision of the doping level in both lightly and heavily doped QDs. The doping strategies currently available, however, operate at the ensemble level, resulting in a Poisson distribution of impurities across the QD population. To date, the synthesis of monodisperse ensembles of QDs individually doped with an identical number of impurity atoms is still an open challenge, and its achievement would enable the realization of advanced QD devices, such as optically/electrically controlled magnetic memories and intragap state transistors and solar cells, that rely on the precise tuning of the impurity states (i.e., number of unpaired spins, energy and width of impurity levels) within the QD host. The only approach reported to date relies on QD seeding with organometallic precursors that are intrinsically unstable and strongly affected by chemical or environmental degradation, which prevents the concept from reaching its full potential and makes the method unsuitable for aqueous synthesis routes. Here, we overcome these issues by demonstrating a doping strategy that bridges two traditionally orthogonal nanostructured material systems, namely, QDs and metal quantum clusters composed of a “magic number” of atoms held together by stable metal-to-metal bonds. Specifically, we use clusters composed of four copper atoms (Cu4) capped with d-penicillamine to seed the growth of CdS QDs in water at room temperature. The elemental analysis, performed by electrospray ionization mass spectrometry, X-ray fluorescence, and inductively coupled plasma mass spectrometry, side by side with optical spectroscopy and transmission electron microscopy measurements, indicates that each Cu:CdS QD in the ensemble incorporates four Cu atoms originating from one Cu4cluster, which acts as a “quantized” source of dopant impurities.

The development of large-scale production methods of two-dimensional (2D) crystals, with on-demand control of the area and thickness, is mandatory to fulfill the potential applications of such materials for photovoltaics. Inverted bulk heterojunction (BHJ) organic solar cell (OSC), which exploits a polymer–fullerene binary blend as the active material, is one potentially important application area for 2D crystals. A large ongoing effort is indeed currently devoted to the introduction of 2D crystals in the binary blend to improve the charge transport properties. While it is expected that the nanoscale domains size of the different components of the blend will significantly impact the performance of the OSC, to date, there is no evidence of quantitative information on the interplay between 2D crystals and fullerene domains size. Here, we demonstrate that by matching the size of WSe2few-layer 2D crystals, produced by liquid-phase exfoliation, with that of the PC71BM fullerene domain in BHJ OSCs, we obtain power conversion efficiencies (PCEs) of ∼9.3%, reaching a 15% improvement with respect to standard binary devices (PCE = 8.10%), i.e., without the addition of WSe2flakes. This is the highest ever reported PCE for 2D material-based OSCs, obtained thanks to the enhanced exciton generation and exciton dissociation at the WSe2-fullerene interface and also electron extraction to the back metal contact as a consequence of a balanced charge carriers mobility. These results push forward the implementation of transition-metal dichalcogenides to boost the performance of BHJ OSCs.

An increasing number of studies have recently reported the rapid degradation of hybrid and all-inorganic lead halide perovskite nanocrystals under electron beam irradiation in the transmission electron microscope, with the formation of nanometer size, high contrast particles. The nature of these nanoparticles and the involved transformations in the perovskite nanocrystals are still a matter of debate. Herein, we have studied the effects of high energy (80/200 keV) electron irradiation on colloidal cesium lead bromide (CsPbBr3) nanocrystals with different shapes and sizes, especially 3 nm thick nanosheets, a morphology that facilitated the analysis of the various ongoing processes. Our results show that the CsPbBr3nanocrystals undergo a radiolysis process, with electron stimulated desorption of a fraction of bromine atoms and the reduction of a fraction of Pb2+ions to Pb0. Subsequently Pb0atoms diffuse and aggregate, giving rise to the high contrast particles, as previously reported by various groups. The diffusion is facilitated by both high temperature and electron beam irradiation. The early stage Pb nanoparticles are epitaxially bound to the parent CsPbBr3lattice, and evolve into nonepitaxially bound Pb crystals upon further irradiation, leading to local amorphization and consequent dismantling of the CsPbBr3lattice. The comparison among CsPbBr3nanocrystals with various shapes and sizes evidences that the damage is particularly pronounced at the corners and edges of the surface, due to a lower diffusion barrier for Pb0on the surface than inside the crystal and the presence of a larger fraction of under-coordinated atoms.

We report the synthesis and catalytic properties of single-walled carbon nanotubepolyamidoamine dendrimers hybrids (SWCNT–PAMAM), prepared viaa convergent strategy. The direct reaction of cystamine-based PAMAM dendrimers (generations 2.5 and 3.0) with pristine SWCNTs in refluxing toluene, followed by immobilization and reduction of [PdCl4]2–, led to the formation of highly dispersed small palladium nanoparticles homogeneously confined throughout the nanotube length. One of these functional materials proved to be an efficient catalyst in Suzuki and Heck reactions, able to promote the above processes down to 0.002 mol % showing a turnover number (TON) of 48 000 and a turnover frequency (TOF) of 566 000 h–1. In addition, the hybrid material could be recovered and recycled for up to 6 times. No leaching of the metal has been detected during the Suzuki coupling. Additional experiments carried out on the spent catalyst permitted to suggest that a “release and catch” mechanism is operative in both reactions, although during Heck reaction small catalytically active soluble Pd species are also present.

Graphene offers promising advantages for biomedical applications. However, adoption of graphene technology in biomedicine also poses important challenges in terms of understanding cell responses, cellular uptake, or the intracellular fate of soluble graphene derivatives. In the biological microenvironment, graphene nanosheets might interact with exposed cellular and subcellular structures, resulting in unexpected regulation of sophisticated biological signaling. More broadly, biomedical devices based on the design of these 2D planar nanostructures for interventions in the central nervous system require an accurate understanding of their interactions with the neuronal milieu. Here, we describe the ability of graphene oxide nanosheets to down-regulate neuronal signaling without affecting cell viability.

The self-organization of nanocrystals has proven to be a versatile route to achieve increasingly sophisticated structures of materials, where the shape and properties of individual particles impact the final functionalities. Recent works have addressed this topic by combining various shapes to achieve more complex arrangements of particles than are possible in single-component samples. However, the ability to create intricate architectures over large regions by exploiting the shape of multiply branched nanocrystals to host a second component remains unexplored. Here, we show how the concave shape of a branched nanocrystal, the so-called octapod, is able to anchor a sphere. The two components self-assemble into a locally ordered monolayer consisting of an intercalated square lattice of octapods and spheres, which is reminiscent of the “tic-tac-toe” game. These tic-tac-toe domains form through an interfacial self-assembly that occurs by the dewetting of a hexane layer containing both particle types. By varying the experimental conditions and performing molecular dynamics simulations, we show that the ligands coating the octapods are crucial to the formation of this structure. We find that the tendency of an octapod to form an interlocking-type structure with a second octapod strongly depends on the ligand shell of the pods. Breaking this tendency by ligand exchange allows the octapods to assemble into a more relaxed configuration, which is able to form a lock-and-key-type structure with a sphere, when they have a suitable size ratio. Our findings provide an example of a more versatile use of branched nanocrystals in self-assembled functional materials.

Colloidal quantum dots (QDs) show great promise as LED phosphors due to their tunable narrow-band emission and ability to produce high-quality white light. Currently, the most suitable QDs for lighting applications are based on cadmium, which presents a toxicity problem for consumer applications. The most promising cadmium-free candidate QDs are based on InP, but their quality lags much behind that of cadmium based QDs. This is not only because the synthesis of InP QDs is more challenging than that of Cd-based QDs, but also because the large lattice parameter of InP makes it difficult to grow an epitaxial, defect-free shell on top of such material. Here, we propose a viable approach to overcome this problem by alloying InP nanocrystals with Zn2+ions, which enables the synthesis of InxZnyP alloy QDs having lattice constant that can be tuned from 5.93 Å (pure InP QDs) down to 5.39 Å by simply varying the concentration of the Zn precursor. This lattice engineering allows for subsequent strain-free, epitaxial growth of a ZnSezS1–zshell with lattice parameters matching that of the core. We demonstrate, for a wide range of core and shell compositions (i.e., varying x, y, and z), that the photoluminescence quantum yield is maximal (up to 60%) when lattice mismatch is minimal.

Among the different synthesis approaches to colloidal nanocrystals, a recently developed toolkit is represented by cation exchange reactions, where the use of template nanocrystals gives access to materials that would be hardly attainable viadirect synthesis. Besides, postsynthetic treatments, such as thermally activated solid-state reactions, represent a further flourishing route to promote finely controlled cation exchange. Here, we report that, upon in situheating in a transmission electron microscope, Cu2Se or Cu nanocrystals deposited on an amorphous solid substrate undergo partial loss of Cu atoms, which are then engaged in local cation exchange reactions with Cu “acceptor” phases represented by rod- and wire-shaped CdSe nanocrystals. This thermal treatment slowly transforms the initial CdSe nanocrystals into Cu2–xSe nanocrystals, through the complete sublimation of Cd and the partial sublimation of Se atoms. Both Cu “donor” and “acceptor” particles were not always in direct contact with each other; hence, the gradual transfer of Cu species from Cu2Se or metallic Cu to CdSe nanocrystals was mediated by the substrate and depended on the distance between the donor and acceptor nanostructures. Differently from what happens in the comparably faster cation exchange reactions performed in liquid solution, this study shows that slow cation exchange reactions can be performed at the solid state and helps to shed light on the intermediate steps involved in such reactions.

Films of colloidal CsPbX3(X = I, Br or Cl) nanocrystals, prepared by solution drop-casting or spin-coating on a silicon substrate, were exposed to a low flux of X-rays from an X-ray photoelectron spectrometer source, causing intermolecular CC bonding of the organic ligands that coat the surface of the nanocrystals. This transformation of the ligand shell resulted in a greater stability of the film, which translated into the following features: (i) Insolubility of the exposed regions in organic solvents which caused instead complete dissolution of the unexposed regions. This enabled the fabrication of stable and strongly fluorescent patterns over millimeter scale areas. (ii) Inhibition of the irradiated regions toward halide anion exchange reactions, when the films were exposed either to halide anions in solution or to hydrohalic vapors. This feature was exploited to create patterned regions of different CsPbIxBryClzcompositions, starting from a film with homogeneous CsPbX3composition. (iii) Resistance of the films to degradation caused by exposure to air and moisture, which represents one of the major drawbacks for the integration of these materials in devices. (iv) Stability of the film in water and biological buffer, which can open interesting perspectives for applications of halide perovskite nanocrystals in aqueous environments.

Neural-interfaces rely on the ability of electrodes to transduce stimuli into electrical patterns delivered to the brain. In addition to sensitivity to the stimuli, stability in the operating conditions and efficient charge transfer to neurons, the electrodes should not alter the physiological properties of the target tissue. Graphene is emerging as a promising material for neuro-interfacing applications, given its outstanding physico-chemical properties. Here, we use graphene-based substrates (GBSs) to interface neuronal growth. We test our GBSs on brain cell cultures by measuring functional and synaptic integrity of the emerging neuronal networks. We show that GBSs are permissive interfaces, even when uncoated by cell adhesion layers, retaining unaltered neuronal signaling properties, thus being suitable for carbon-based neural prosthetic devices.

Carbon nanotubes and graphene possess a unique extended π-system that makes them stand out among carbon nanostructures. The resulting electronic properties enable electron or charge flow along one or two directions, respectively, thus offering the opportunity to connect electronically different entities that come into contact, be they living cells or catalytic systems. Using these carbon nanostructures thus holds great promise in providing innovative solutions to address key challenges in the fields of medicine and energy. Here, we discuss how chemical functionalization of these carbon nanostructures is a crucial tool to master their properties and deliver innovation.

We report on pyramid-shaped wurtzite cadmium selenide (CdSe) nanocrystals (NCs), synthesized by hot injection in the presence of chloride ions as shape-directing agents, exhibiting reversed crystal polarity compared to former reports. Advanced transmission electron microscopy (TEM) techniques (image-corrected high-resolution TEM with exit wave reconstruction and probe-corrected high-angle annular dark field-scanning TEM) unequivocally indicate that the triangular base of the pyramids is the polar (0001̅) facet and their apex points toward the [0001] direction. Density functional theory calculations, based on a simple model of binding of Cl–ions to surface Cd atoms, support the experimentally evident higher thermodynamic stability of the (0001̅) facet over the (0001) one conferred by Cl–ions. The relative stability of the two polar facets of wurtzite CdSe is reversed compared to previous experimental and computational studies on Cd chalcogenide NCs, in which no Cl-based chemicals were deliberately used in the synthesis or no Cl–ions were considered in the binding models. Self-assembly of these pyramids in a peculiar clover-like geometry, triggered by the addition of oleic acid, suggests that the basal (polar) facet has a density and perhaps type of ligands significantly different from the other three facets, since the pyramids interact with each other exclusively viatheir lateral facets. A superstructure, however with no long-range order, is observed for clovers with their (0001̅) facets roughly facing each other. The CdSe pyramids were also exploited as seeds for CdS pods growth, and the peculiar shape of the derived branched nanostructures clearly arises from the inverted polarity of the seeds.

Surface tunability and their ability to translocate plasma membranes make chemically functionalized carbon nanotubes (f-CNTs) promising intracellular delivery systems for therapeutic or diagnostic purposes in the central nervous system (CNS). The present study aimed to determine the biological impact of different types of multiwalled CNTs (MWNTs) on primary neuronal and glial cell populations isolated from fetal rat frontal cortex (FCO) and striatum (ST). Neurons from both brain regions were generally not affected by exposure to MWNTs as determined by a modified LDH assay. In contrast, the viability of mixed glia was reduced in ST-derived mixed glial cultures, but not in FCO-derived ones. Cytotoxicity was independent of MWNT type or dose, suggesting an inherent sensitivity to CNTs. Characterization of the cell populations in mixed glial cultures prior to nanotube exposure showed higher number of CD11b/c positive cells in the ST-derived mixed glial cultures. After exposure to MWNTs, CNT were uptaken more effectively by CD11b/c positive cells (microglia), compared to GFAP positive cells (astrocytes). When exposed to conditioned media from microglia enriched cultures exposed to MWNTs, ST-derived glial cultures secreted more NO than FCO-derived cells. These results suggested that the more significant cytotoxic response obtained from ST-derived mixed glia cultures was related to the higher number of microglial cells in this brain region. Our findings emphasize the role that resident macrophages of the CNS play in response to nanomaterials and the need to thoroughly investigate the brain region-specific effects toward designing implantable devices or delivery systems to the CNS.

Considerable progress in the synthesis and technology of hydrogels makes these materials attractive structures for designing controlled-release drug delivery systems. In particular, this review highlights the latest advances in nanocomposite hydrogels as drug delivery vehicles. The inclusion/incorporation of nanoparticles in three-dimensional polymeric structures is an innovative means for obtaining multicomponent systems with diverse functionality within a hybrid hydrogel network. Nanoparticle-hydrogel combinations add synergistic benefits to the new 3D structures. Nanogels as carriers for cancer therapy and injectable gels with improved self-healing properties have also been described as new nanocomposite systems.

We present an approach for the synthesis of ternary copper indium sulfide (CIS) and quaternary copper indium zinc sulfide (CIZS) nanocrystals (NCs) by means of partial cation exchange with In3+and Zn2+. The approach consists of a sequential three-step synthesis: first, binary Cu2S NCs were synthesized, followed by the homogeneous incorporation of In3+by an in situpartial cation-exchange reaction, leading to CIS NCs. In the last step, a second partial exchange was performed where Zn2+partially replaced the Cu+and In3+cations at the surface, creating a ZnS-rich shell with the preservation of the size and shape. By careful tuning reaction parameters (growth and exchange times as well as the initial Cu+:In3+:Zn2+ratios), control over both the size and composition was achieved. This led to a broad tuning of photoluminescence of the final CIZS NCs, ranging from 880 to 1030 nm without altering the NCs size. Cytotoxicity tests confirmed the biocompatibility of the synthesized CIZS NCs, which opens up opportunities for their application as near-infrared fluorescent markers in the biomedical field.

We report the synthesis of alloyed quaternary and quinary nanocrystals based on copper chalcogenides, namely, copper zinc selenide–sulfide (CZSeS), copper tin selenide–sulfide (CTSeS), and copper zinc tin selenide–sulfide (CZTSeS) nanoplatelets (NPLs) (∼20 nm wide) with tunable chemical composition. Our synthesis scheme consisted of two facile steps: i.e., the preparation of copper selenide–sulfide (Cu2–xSeyS1–y) platelet shaped nanocrystals viathe colloidal route, followed by an in situcation exchange reaction. During the latter step, the cation exchange proceeded through a partial replacement of copper ions by zinc or/and tin cations, yielding homogeneously alloyed nanocrystals with platelet shape. Overall, the chemical composition of the alloyed nanocrystals can easily be controlled by the amount of precursors that contain cations of interest (e.g., Zn, Sn) to be incorporated/alloyed. We have also optimized the reaction conditions that allow a complete preservation of the size, morphology, and crystal structure as that of the starting Cu2–xSeyS1–yNPLs. The alloyed NPLs were characterized by optical spectroscopy (UV–vis–NIR) and cyclic voltammetry (CV), which demonstrated tunability of their light absorption characteristics as well as their electrochemical band gaps.

A ball-milling treatment can be employed to exfoliate graphite through interactions with commercially available melamine under solid conditions. This procedure allows the fast production of relatively large quantities of material with a low presence of defects. The milling treatment can be modulated in order to achieve graphene flakes with different sizes. Once prepared, the graphene samples can be redispersed in organic solvents, water, or culture media, forming stable dispersions that can be used for multiple purposes. In the present work, we have screened electron-rich benzene derivatives along with triazine derivatives in their respective ability to exfoliate graphite. The results suggest that the formation of a hydrogen-bonding network is important for the formation of multipoint interactions with the surfaces of graphene, which can be used for the exfoliation of graphite and the stabilization of graphene in different solvents. Aminotriazine systems were found to be the best partners in the preparation and stabilization of graphene layers in different solvents, while the equivalent benzene derivatives did not show comparable exfoliation ability. Computational studies have also been performed to rationalize the experimental results. The results provide also the basis for further work in the preparation of noncovalently modified graphene, where derivatives of aminotriazines can be designed to form extensive hydrogen-bond 2D networks on the graphene surface with the aim of manipulating their electronic and chemical properties.

Myocardial tissue engineering currently represents one of the most realistic strategies for cardiac repair. We have recently discovered the ability of carbon nanotube scaffolds to promote cell division and maturation in cardiomyocytes. Here, we test the hypothesis that carbon nanotube scaffolds promote cardiomyocyte growth and maturation by altering the gene expression program, implementing the cell electrophysiological properties and improving networking and maturation of functional syncytia. In our study, we combine microscopy, biological and electrophysiological methodologies, and calcium imaging, to verify whether neonatal rat ventricular myocytes cultured on substrates of multiwall carbon nanotubes acquire a physiologically more mature phenotype compared to control (gelatin). We show that the carbon nanotube substrate stimulates the induction of a gene expression profile characteristic of terminal differentiation and physiological growth, with a 2-fold increase of α-myosin heavy chain (P< 0.001) and upregulation of sarcoplasmic reticulum Ca2+ATPase 2a. In contrast, markers of pathological hypertrophy remain unchanged (β-myosin heavy chain, skeletal α-actin, atrial natriuretic peptide). These modifications are paralleled by an increase of connexin-43 gene expression, gap junctions and functional syncytia. Moreover, carbon nanotubes appear to exert a protective effect against the pathologic stimulus of phenylephrine. Finally, cardiomyocytes on carbon nanotubes demonstrate a more mature electrophysiological phenotype of syncytia and intracellular calcium signaling. Thus, carbon nanotubes interacting with cardiomyocytes have the ability to promote physiological growth and functional maturation. These properties are unique in the current vexing field of tissue engineering, and offer unprecedented perspectives in the development of innovative therapies for cardiac repair.

The artificial leaf project calls for new materials enabling multielectron catalysis with minimal overpotential, high turnover frequency, and long-term stability. Is graphene a better material than carbon nanotubes to enhance water oxidation catalysis for energy applications? Here we show that functionalized graphene with a tailored distribution of polycationic, quaternized, ammonium pendants provides an sp2carbon nanoplatform to anchor a totally inorganic tetraruthenate catalyst, mimicking the oxygen evolving center of natural PSII. The resulting hybrid material displays oxygen evolution at overpotential as low as 300 mV at neutral pH with negligible loss of performance after 4 h testing. This multilayer electroactive asset enhances the turnover frequency by 1 order of magnitude with respect to the isolated catalyst, and provides a definite up-grade of the carbon nanotube material, with a similar surface functionalization. Our innovation is based on a noninvasive, synthetic protocol for graphene functionalization that goes beyond the ill-defined oxidation–reduction methods, allowing a definite control of the surface properties.

We studied the influence of chloride ions (Cl–), introduced as CdCl2, on the seeded growth synthesis of colloidal branched CdSe(core)/CdS(pods) nanocrystals. This is carried out by growing wurtzite CdS pods on top of preformed octahedral sphalerite CdSe seeds. When no CdCl2is added, the synthesis of multipods has a low reproducibility, and the side nucleation of CdS nanorods is often observed. At a suitable concentration of CdCl2, octapods are formed and they are stable in solution during the synthesis. Our experiments indicate that Cl–ions introduced in the reaction reduce the availability of Cd2+ions in solution, most likely viaformation of strong complexes with both Cd and the various surfactants. This prevents homogeneous nucleation of CdS nanocrystals, so that the heterogeneous nucleation of CdS pods on top of the CdSe seeds is the preferred process. Once such optimal concentration of CdCl2is set for a stable growth of octapods, the pod lengths can be tuned by varying the relative ratios of the various alkyl phosphonic acids used. Furthermore, at higher concentrations of CdCl2added, octapods are initially formed, but many of them evolve into tetrapods over time. This transformation points to an additional role of Cl species in regulating the growth rate and stability of various crystal facets of the CdS pods.

Marine toxins appear to be increasing in many areas of the world. An emerging problem in the Mediterranean Sea is represented by palytoxin (PlTX), one of the most potent marine toxins, frequently detected in seafood. Due to the high potential for human toxicity of PlTX, there is a strong and urgent need for sensitive methods toward its detection and quantification. We have developed an ultrasensitive electrochemiluminescence-based sensor for the detection of PlTX, taking advantage of the specificity provided by anti-PlTX antibodies, the good conductive properties of carbon nanotubes, and the excellent sensitivity achieved by a luminescence-based transducer. The sensor was able to produce a concentration-dependent light signal, allowing PlTX quantification in mussels, with a limit of quantification (LOQ = 2.2 μg/kg of mussel meat) more than 2 orders of magnitude more sensitive than that of the commonly used detection techniques, such as LC-MS/MS.

New developments in nanotechnology are increasingly designed to modulate relevant interactions between nanomaterials and neurons, with the aim of exploiting the physical properties of synthetic materials to tune desired and specific biological processes. Carbon nanotubes have been applied in several areas of nerve tissue engineering to study cell behavior or to instruct the growth and organization of neural networks. Recent reports show that nanotubes can sustain and promote electrical activity in networks of cultured neurons. However, such results are usually limited to carbon nanotube/neuron hybrids formed on a monolayer of dissociated brain cells. In the present work, we used organotypic spinal slices to model multilayer tissue complexity, and we interfaced such spinal segments to carbon nanotube scaffolds for weeks. By immunofluorescence, scanning and transmission electronic microscopy, and atomic force microscopy, we investigated nerve fiber growth when neuronal processes exit the spinal explant and develop in direct contact to the substrate. By single-cell electrophysiology, we investigated the synaptic activity of visually identified ventral interneurons, within the ventral area of the explant, thus synaptically connected, but located remotely, to the substrate/network interface. Here we show that spinal cord explants interfaced for weeks to purified carbon nanotube scaffolds expand more neuronal fibers, characterized by different mechanical properties and displaying higher growth cones activity. On the other hand, exploring spontaneous and evoked synaptic activity unmasks an increase in synaptic efficacy in neurons located at as far as 5 cell layers from the cell–substrate interactions.

In a set of unprecedented experiments combining “bottom-up” and “top-down” approaches, we report the engineering of patterned surfaces in which functionalized MWCNTs have been selectively adsorbed on polymeric matrices as obtained by microlithographic photo-cross-linking of polystyrene polymers bearing 2,6-di(acetylamino)-4-pyridyl moieties (PS1) deposited on glass or Si. All patterned surfaces have been characterized by optical, fluorescence, and SEM imaging techniques, showing the local confinement of the CNTs materials on the polymeric microgrids. These results open new possibilities toward the controlled manipulation of CNTs on surfaces, using H-bonding self-assembly as the main driving force.

Amphotericin B (AMB) has long been considered the most effective drug in the treatment of serious invasive fungal infections. There are, however, major limitations to its use, due to several adverse effects, including acute infusional reactions and, most relevant, a dose-dependent nephrotoxicity. At least some of these effects are attributed to the aggregation of AMB as a result of its poor water solubility. To overcome this problem, reformulated versions of the drug have been developed, including a micellar dispersion of AMB with sodium deoxycholate (AMBD), its encapsulation into liposomes, or its incorporation into lipidic complexes. The development of nanobiotechnologies provides novel potential drug delivery systems that make use of nanomaterials such as functionalized carbon nanotubes (f-CNTs), which are emerging as an innovative and efficient tool for the transport and cellular translocation of therapeutic molecules. In this study, we prepared two conjugates between f-CNTs and AMB. The antifungal activity of these conjugates was tested against a collection of reference and clinical fungal strains, in comparison to that of AMB alone or AMBD. Measured minimum inhibition concentration (MIC) values for f-CNT−AMB conjugates were either comparable to or better than those displayed by AMB and AMBD. Furthermore, AMBD-resistant Candidastrains were found to be susceptible to f-CNT−AMB 1. Additional studies, aimed at understanding the mechanism of action of the conjugates, suggest a nonlytic mechanism, since the compounds show a major permeabilizing effect on the tested fungal strains only after extended incubation. Interestingly, the f-CNT−AMB 1does not show any significant toxic effect on Jurkat cells at antifungal concentrations.

Novel applications of single-walled carbon nanotubes (SWNT) rely on the development of new strategies to make them easier to handle without affecting their structural properties. In this work, we have selectively deposited Au nanoparticles (Au NP) on SWNT assisted by UV light irradiation. XPS analysis and UV−vis spectroscopy indicate that the deposition occurs at the defects generated after oxidation of the SWNT. By addition of n-dodecylthiol, the separation of oxidized tubes with Au NP (Au-ox-SWNT) from tubes devoid of Au NP (bare tubes, b-SWNT) was achieved. Raman and UV−vis−NIR spectra indicate that UV irradiation induces a faster nucleation of Au NP on metallic SWNT. This new technique can be useful for the preparation of nanohybrid composites with enhanced properties, as increased thermal stability, and to obtain purified SWNT.

Few-layer graphenes (FLG) produced by dispersion and exfoliation of graphite in N-methylpyrrolidone were successfully functionalized using the 1,3-dipolar cycloaddition of azomethine ylides. The amino functional groups attached to graphene sheets were quantified by the Kaiser test. These amino groups selectively bind to gold nanorods, which were introduced as contrast markers for the identification of the graphene reactive sites. The interaction between gold nanorods and functionalized graphene was followed by UV−vis spectroscopy. The presence of the organic groups was confirmed by X-ray photoelectron spectroscopy and thermogravimetric analysis. The sheets were characterized by transmission electron microscopy, demonstrating the presence of gold nanorods distributed uniformly all over the graphene surface. This observation indicates that reaction has taken place not just at the edges but also at the internal CC bonds of graphene. Our results identify exfoliated graphene as a considerably more reactive structure than graphite and hence open the possibility to control the functionalization for use as a scaffold in the construction of organized composite nanomaterials.

Functionalized carbon nanotube (CNT) derivatives are currently under thorough investigation in different biomedical investigations. In this field of research, the composition of sample either in terms of covalently attached or physisorbed moieties can greatly affect the observed results and hamper the comparison between different studies. Therefore, the availability of a fast and reliable analytical technique to assess both the type of interaction (covalent vsnoncovalent) and the composition of CNT conjugates is of great importance. Here we describe that the two-dimensional diffusion-ordered (DOSY) NMR spectroscopy is extremely useful to discriminate between conjugated and unconjugated polyethylene glycol groups in samples obtained by condensation with oxidized single-walled carbon nanotubes (SWNTs). This fast and nondestructive technique allows us to follow the removal of unconjugated polyethylene glycol chains during the purification. In particular, DOSY analysis reveal that about 1/3(wt %) of the polyethylene glycol used for the condensation remained physisorbed to functionalized SWNTs after dialysis. Complete elimination of physisorbed polyethylene glycol was achieved using diafiltration.

In this paper, we report the functionalization of the surface of multiwalled carbon nanotubes (MWNTs) with Au dendrimer encapsulated nanoparticles (DENs). The results show that, when pristine MWNTs having hydrophobic surfaces are exposed to DENs, the dendrimers aggregate on the MWNT surface. However, when the MWNTs are oxidized in acid prior to exposure to DENs, well-dispersed submonolayer coverages of Au nanoparticles are observed on the MWNT surface. This suggests that acid-induced debundling of the nanotubes is an essential prerequisite for attachment of nearly monodisperse DENs. Electron microscopy and NMR spectroscopy confirm that the structures of the DENs and dendrimers are retained after immobilization on the surface of acid-functionalized MWNTs.

The interaction of microwaves with carbon nanotubes (CNTs) is an interesting topic for a variety of potential applications. Microwaves have been used for the purification of CNTs and for their chemical functionalization, providing a technique for simple, green, and large-scale protocols. In addition, the selective destruction of metallic CNTs under microwave irradiation could potentially result in a batch of semiconducting-only nanotubes. As an innovative application, the combination of microwaves with well-aligned CNTs could produce a new illumination technology. Moreover, the microwave absorbing properties of CNTs and their different behavior from typical organic compounds may open the door to the preparation of a wide range of new materials useful in many fields. A few examples of practical applications include electromagnetic interference for protecting the environment from radiation and microwave hyperthermia for cancer treatment as well as other medical therapies requiring precise heating of biological tissues.

Novel colloidal composites have been designed to incorporate multiple functionalities that allow optical detection, magnetic manipulation, molecular trapping, and thermal response. Such particles are made of gold nanoparticle cores covered by a thin layer of metallic nickel and a poly(N-isopropylacrylamide) (pNIPAM) shell. While the gold cores provide efficient optical response through localized surface plasmon resonances, nickel allows external magnetic manipulation and the pNIPAM shell can be swollen or collapsed as a function of temperature, thus allowing capture and release of various types of molecules.

The preparation of bulk quantities of 13C-labeled graphene materials is relevant for basic investigations and for practical applications. In addition, 13C-labeled graphene materials can be very useful in biological and environmental studies, as they may allow the detection of graphene or its derivatives in cells or organs. In this paper, we describe the synthesis of 13C-labeled graphene materials (few-layer graphene, FLG, and graphene oxide, GO) on a tens of mg scale, starting from 13C-labeled methane to afford carbon fibers, followed by liquid-phase exfoliation (FLG) or oxidation (GO). The materials have been characterized by several analytical and microscopic techniques, including Raman and nuclear magnetic resonance spectroscopies, thermogravimetric analysis, X-ray photoelectron spectroscopy, and X-ray powder diffraction. As a proof of concept, the distribution of the title compounds in cells has been investigated. In fact, the analysis of the 13C/12C ratio with isotope ratio mass spectrometry (IRMS) allows the detection and quantification of very small amounts of material in cells or biological compartments with high selectivity, even when the material has been degraded. During the treatment of 13C-labeled FLG with HepG2 cells, 4.1% of the applied dose was found in the mitochondrial fraction, while 4.9% ended up in the nuclear fraction. The rest of the dose did not enter into the cell and remained in the plasma membrane or in the culture media.