Advanced 1D heterostructures based on nanotube templates and molecules.

Recent advancements in materials science have shed light on the potential of exploring hierarchical assemblies of molecules on surfaces, driven by both fundamental and applicative challenges. This field encompasses diverse areas including molecular storage, drug delivery, catalysis, and nanoscale chemical reactions. In this context, the utilization of nanotube templates (NTs) has emerged as promising platforms for achieving advanced one-dimensional (1D) molecular assemblies. NTs offer cylindrical, crystalline structures with high aspect ratios, capable of hosting molecules both externally and internally (Mol@NT). Furthermore, NTs possess a wide array of available diameters, providing tunability for tailored assembly. This review underscores recent breakthroughs in the field of Mol@NT. The first part focuses on the diverse panorama of structural properties in Mol@NT synthesized in the last decade. The advances in understanding encapsulation, adsorption, and ordering mechanisms are detailed. In a second part, the review highlights the physical interactions and photophysics properties of Mol@NT obtained by the confinement of molecules and nanotubes in the van der Waals distance regime. The last part of the review describes potential applicative fields of these 1D heterostructures, providing specific examples in photovoltaics, luminescent materials, and bio-imaging. A conclusion gathers current challenges and perspectives of the field to foster discussion in related communities.

Study of Ion-to-Electron Transducing Layers for the Detection of Nitrate Ions Using FPSX(TDDAN)-Based Ion-Sensitive Electrodes.

The development of ISE-based sensors for the analysis of nitrates in liquid phase is described in this work. Focusing on the tetradodecylammonium nitrate (TDDAN) ion exchanger as well as on fluoropolysiloxane (FPSX) polymer-based layers, electrodeposited matrixes containing double-walled carbon nanotubes (DWCNTs), embedded in either polyethylenedioxythiophene (PEDOT) or polypyrrole (PPy) polymers, ensured improved ion-to-electron transducing layers for NO3- detection. Thus, FPSX-based pNO3-ElecCell microsensors exhibited good detection properties (sensitivity up to 55 mV/pX for NO3 values ranging from 1 to 5) and acceptable selectivity in the presence of the main interferent anions (Cl-, HCO3-, and SO42-). Focusing on the temporal drift bottleneck, mixed results were obtained. On the one hand, relatively stable measurements and low temporal drifts (~1.5 mV/day) were evidenced on several days. On the other hand, the pNO3 sensor properties were degraded in the long term, being finally characterized by high response times, low detection sensitivities, and important measurement instabilities. These phenomena were related to the formation of some thin water-based layers at the polymer-metal interface, as well as the physicochemical properties of the TDDAN ion exchanger in the FPSX matrix. However, the improvements obtained thanks to DWCNT-based ion-to-electron transducing layers pave the way for the long-term analysis of NO3- ions in real water-based solutions.

Interactions of Graphene Oxide and Few-Layer Graphene with the Blood-Brain Barrier.

Thanks to their biocompatibility and high cargo capability, graphene-based materials (GRMs) might represent an ideal brain delivery system. The capability of GRMs to reach the brain has mainly been investigated in vivo and has highlighted some controversy. Herein, we employed two in vitro BBB models of increasing complexity to investigate the bionano interactions with graphene oxide (GO) and few-layer graphene (FLG): a 2D murine Transwell model, followed by a 3D human multicellular assembloid, to mimic the complexity of the in vivo architecture and intercellular crosstalk. We developed specific methodologies to assess the translocation of GO and FLG in a label-free fashion and a platform applicable to any nanomaterial. Overall, our results show good biocompatibility of the two GRMs, which did not impact the integrity and functionality of the barrier. Sufficiently dispersed subpopulations of GO and FLG were actively uptaken by endothelial cells; however, the translocation was identified as a rare event.

International Interlaboratory Comparison of Thermogravimetric Analysis of Graphene-Related Two-Dimensional Materials.

Research on graphene-related two-dimensional (2D) materials (GR2Ms) in recent years is strongly moving from academia to industrial sectors with many new developed products and devices on the market. Characterization and quality control of the GR2Ms and their properties are critical for growing industrial translation, which requires the development of appropriate and reliable analytical methods. These challenges are recognized by International Organization for Standardization (ISO 229) and International Electrotechnical Commission (IEC 113) committees to facilitate the development of these methods and standards which are currently in progress. Toward these efforts, the aim of this study was to perform an international interlaboratory comparison (ILC), conducted under Versailles Project on Advanced Materials and Standards (VAMAS) Technical Working Area (TWA) 41 "Graphene and Related 2D Materials" to evaluate the performance (reproducibility and confidence) of the thermogravimetric analysis (TGA) method as a potential new method for chemical characterization of GR2Ms. Three different types of representative and industrially manufactured GR2Ms samples, namely, pristine few-layer graphene (FLG), graphene oxide (GO), and reduced graphene oxide (rGO), were used and supplied to ILC participants to complete the study. The TGA method performance was evaluated by a series of measurements of selected parameters of the chemical and physical properties of these GR2Ms including the number of mass loss steps, thermal stability, temperature of maximum mass change rate (Tp) for each decomposition step, and the mass contents (%) of moisture, oxygen groups, carbon, and impurities (organic and non-combustible residue). TGA measurements determining these parameters were performed using the provided optimized TGA protocol on the same GR2Ms by 12 participants across academia, industry stakeholders, and national metrology institutes. This paper presents these results with corresponding statistical analysis showing low standard deviation and statistical conformity across all participants that confirm that the TGA method can be satisfactorily used for characterization of these parameters and the chemical characterization and quality control of GR2Ms. The common measurement uncertainty for each parameter, key contribution factors were identified with explanations and recommendations for their elimination and improvements toward their implementation for the development of the ISO/IEC standard for chemical characterization of GR2Ms.

Nose-only inhalations of high-dose alumina nanoparticles/hydrogen chloride gas mixtures induce strong pulmonary pro-inflammatory response: a pilot study.

OBJECTIVE: Solid composite propellants combustion, in aerospace and defense fields, can lead to complex aerosols emission containing high concentrations of alumina nanoparticles (Al2O3 NPs) and hydrogen chloride gas (HClg). Exposure to these mixtures by inhalation is thus possible but literature data toward their pulmonary toxicity are missing. To specify hazards resulting from these combustion aerosols, a pilot study was implemented. MATERIALS AND METHODS: Male Wistar rats were nose-only exposed to Al2O3 NPs (primary size 13 nm, 10 g/L suspension leading to 20.0-22.1 mg/m3 aerosol) and/or to HClg aerosols (5 ppm target concentration) following two exposure scenarios (single exposures (SE) or repeated exposures (RE)). Bronchoalveolar lavage fluids (BALF) content and lungs histopathology were analyzed 24 h after exposures. RESULTS: Repeated co-exposures increased total proteins and LDH concentrations in BALF indicating alveolar-capillary barrier permeabilization and cytolysis. Early pulmonary inflammation was induced after RE to Al2O3 NPs ± HClg resulting in PMN, TNF-α, IL-1ß, and GRO/KC increases in BALF. Both exposure scenarios resulted in pulmonary histopathological lesions (vascular congestions, bronchial pre-exfoliations, vascular and interalveolar septum edemas). Lung oxidative damages were observed in situ following SE. CONCLUSION: Observed biological effects are dependent on both aerosol content and exposure scenario. Results showed an important pro-inflammatory effect of Al2O3 NPs/HClg mixtures on the lungs of rat 24 h after exposure. This pilot study raises concerns toward potential long-term pulmonary toxicity of combustion aerosols and highlights the importance for further studies to be led in order to define dose limitations and exposure thresholds for risk management at the work place.

Tuning Magnetic Properties of a Carbon Nanotube-Lanthanide Hybrid Molecular Complex through Controlled Functionalization.

Molecular magnets attached to carbon nanotubes (CNT) are being studied as potential candidates for developing spintronic and quantum technologies. However, the functionalization routes used to develop these hybrid systems can drastically affect their respective physiochemical properties. Due to the complexity of this systems, little work has been directed at establishing the correlation between the degree of functionalization and the magnetic character. Here, we demonstrate the chemical functionalization degree associated with molecular magnet loading can be utilized for controlled tuning the magnetic properties of a CNT-lanthanide hybrid complex. CNT functionalization degree was evaluated by interpreting minor Raman phonon modes in relation to the controlled reaction conditions. These findings were exploited in attaching a rare-earth-based molecular magnet (Gd-DTPA) to the CNTs. Inductively coupled plasma mass spectrometry, time-of-flight secondary ion mass spectrometry and super conducting quantum interference device (SQUID) measurements were used to elucidate the variation of magnetic character across the samples. This controlled Gd-DTPA loading on the CNT surface has led to a significant change in the nanotube intrinsic diamagnetism, showing antiferromagnetic coupling with increase in the Weiss temperature with respect to increased loading. This indicates that synthesis of a highly correlated spin system for developing novel spintronic technologies can be realized through a carbon-based hybrid material.

A Hydrogel/Carbon-Nanotube Needle-Free Device for Electrostimulated Skin Drug Delivery.

The permeability of skin allows passive diffusion across the epidermis to reach blood vessels but this is possible only for small molecules such as nicotine. In order to achieve transdermal delivery of large molecules such as insulin or plasmid DNA, permeability of the skin and mainly the permeability of the stratum corneum skin layer has to be increased. Moreover, alternative routes that avoid the use of needles will improve the quality of life of patients. A method known as electropermeabilisation has been shown to increase skin permeability. Herein, we report the fabrication of an innovative hydrogel made of a nanocomposite material. This nanocomposite device aims to permeabilise the skin and deliver drug molecules at the same time. It includes a biocompatible polymer matrix (hydrogel) and double-walled carbon nanotubes (DWCNTs) in order to bring electrical conductivity and improve mechanical properties. Carbon nanotubes and especially DWCNTs are ideal candidates, combining high electrical conductivity with a very high specific surface area together with a good biocompatibility when included into a material. The preparation and characterization of the nanocomposite hydrogel as well as first results of electrostimulated transdermal delivery using an ex vivo mouse skin model are presented.

Spray-coated carbon nanotube carpets for creeping reduction of conducting polymer based artificial muscles.

During cyclic actuation, conducting polymer based artificial muscles are often creeping from the initial movement range. One of the likely reasons of such behaviour is unbalanced charging during conducting polymer oxidation and reduction. To improve the actuation reversibility and subsequently the long time performance of ionic actuators, we suggest using spray-coated carbon nanotube (CNT) carpets on the surface of the conducting polymer electrodes. We show that carbon nanotubes facilitate a conducting polymer redox reaction and improve its reversibility. Consequently, in the long term, charge accumulation in the polymer film is avoided leading to a significantly improved lifetime performance during cycling actuation. To our knowledge, it is the first time a simple solution to an actuator creeping problem has been suggested.

Surface Area of Carbon Nanoparticles: A Dose Metric for a More Realistic Ecotoxicological Assessment.

Engineered nanoparticles such as graphenes, nanodiamonds, and carbon nanotubes correspond to different allotropes of carbon and are among the best candidates for applications in fast-growing nanotechnology. It is thus likely that they may get into the environment at each step of their life cycle: production, use, and disposal. The aquatic compartment concentrates pollutants and is expected to be especially impacted. The toxicity of a compound is conventionally evaluated using mass concentration as a quantitative measure of exposure. However, several studies have highlighted that such a metric is not the best descriptor at the nanoscale. Here we compare the inhibition of Xenopus laevis larvae growth after in vivo exposure to different carbon nanoparticles for 12 days using different dose metrics and clearly show that surface area is the most relevant descriptor of toxicity for different types of carbon allotropes.

Effectiveness of a two-stage strategy with HPV testing followed by visual inspection with acetic acid for cervical cancer screening in a low-income setting.

The World Health Organization recently advocated a two-stage strategy with human papillomavirus (HPV) testing followed by visual inspection of the cervix with acetic acid (VIA) as a suitable option for cervical cancer screening. However, its accuracy has never been directly assessed in the context of primary screening. To evaluate effectiveness of HPV testing on self-obtained specimens (self-HPV) followed by VIA (sequential testing) in a low-income setting, we recruited 540 women aged between 30 and 65 years in two Cameroonian periurban areas. Eligible women were counseled about cervical cancer and how to perform self-sampling. HPV positive and a random sample of HPV-negative women were called back for VIA and biopsy. Disease was defined by interpretation of cervical intraepithelial neoplasia Grade 2 or worse (CIN2+). Performances of VIA, self-HPV and sequential testing were determined after adjustment for verification bias. HPV prevalence was 27.0%. VIA positivity was 12.9% and disease prevalence was 5%. Sensitivity and specificity of VIA for CIN2+ were 36.4% [95% confidence interval (CI): 15.2-64.6%] and 90.4% (95% CI: 85.4-93.7%), respectively. Sensitivity of self-HPV [100.0% (95% CI: 79.6-100.0%)] was 66% higher than that of sequential testing [33.3% (95% CI: 15.2-58.3%)]. Meanwhile, specificity of self-HPV [74.5% (95% CI: 70.6-78.1%)] was 22% lower than that of sequential testing [96.7% (95% CI: 94.8-97.9%)]. A two-stage screening strategy with self-HPV followed by VIA improves specificity of cervical cancer screening, but at the cost of an important loss of sensitivity. Ways to improve VIA performance or other tools are needed to increase positive predictive value of HPV testing.

Complement activation by carbon nanotubes and its influence on the phagocytosis and cytokine response by macrophages.

Carbon nanotubes (CNTs) have promised a range of applications in biomedicine. Although influenced by the dispersants used, CNTs are recognized by the innate immune system, predominantly by the classical pathway of the complement system. Here, we confirm that complement activation by the CNT used continues up to C3 and C5, indicating that the entire complement system is activated including the formation of membrane-attack complexes. Using recombinant forms of the globular regions of human C1q (gC1q) as inhibitors of CNT-mediated classical pathway activation, we show that C1q, the first recognition subcomponent of the classical pathway, binds CNTs via the gC1q domain. Complement opsonisation of CNTs significantly enhances their uptake by U937 cells, with concomitant downregulation of pro-inflammatory cytokines and up-regulation of anti-inflammatory cytokines in both U937 cells and human monocytes. We propose that CNT-mediated complement activation may cause recruitment of cellular infiltration, followed by phagocytosis without inducing a pro-inflammatory immune response. FROM THE CLINICAL EDITOR: This study highlights the importance of the complement system in response to carbon nanontube administration, suggesting that the ensuing complement activation may cause recruitment of cellular infiltration, followed by phagocytosis without inducing a pro-inflammatory immune response.

Short term exposure to multi-walled carbon nanotubes induce oxidative stress and DNA damage in Xenopus laevis tadpoles.

The potential impact of Multiwalled Carbon NanoTubes (MWCNTs) was investigated on Xenopus laevis tadpoles exposed to 0.1, 1 and 10mg/L. Oxidative stress was measured in entire larvae exposed and DNA damage (Comet assay) was carried out in erythrocytes of circulating blood from 2h to 24h according to standardized recommendations. Results showed significant H2O2 production when larvae were exposed to 1mg/L and 10mg/L of MWCNTs after 4h and 2h of exposure, respectively. Antioxidant enzyme activities showed significant induction of catalase (CAT), glutathione reductase (GR) and superoxide dismutase (SOD) from only 2h of exposure to 10mg/L of MWCNTs. In presence of 1mg/L of MWCNTs, only GR and CAT activities were significantly induced at 4h. Enzyme activities do not follow a simple dose-effect relation, but the time of induction is shortened in relation with the tested concentration. The Comet assay results showed significant DNA damages with a dose dependent response. The profiles of DNA damages show fluctuations, in course of time, which are characteristics of oxidative stress response in relation with the continuous balance between damage and compensation process.

Classification framework for graphene-based materials.

Graphing graphene: Because the naming of graphene-based materials (GBMs) has led to confusion and inconsistency, a classification approach is necessary. Three physical-chemical properties of GBMs have been defined by the GRAPHENE Flagship Project of the European Union for the unequivocal classification of these materials (see grid).

Cellular uptake of multi-walled carbon nanotubes is associated to genotoxic and teratogenic effects towards the freshwater diatom Nitzschia linearis.

The increase in industrial production of multi-walled carbon nanotubes (MWCNTs) raises concerns about their potential adverse effects associated to environmental releases, especially in aquatic environments where they are likely to accumulate. This study focuses on the environmental impact of MWCNTs, specifically on a benthic freshwater diatom (Nitzschia linearis), which plays a major role in the primary production of water bodies. The obtained results indicate that exposure to MWCNTs in the presence of natural organic matter (NOM) inhibits diatom's growth in a dose-dependent manner after 72 h of exposure. Interestingly, the photosystem II quantum yield (PSIIQY) in diatoms remains unaffected even after exposure to MWCNTs at 10 mg/L. After 48 h of exposure, MWCNTs are found to bind preferentially to extracellular polymeric substances (EPS) produced by diatoms, which could decrease their toxicity by limiting their interaction with this organism. However, measurement of genotoxicity and teratogenicity in diatoms exposed to MWCNTs revealed that the exposure to MWCNTs increased the occurrence of cells with micronuclei and abnormal frustules. Microscopy analyses including two-photon excitation microscopy (TPEM) revealed the internalization of MWCNTs. Investigations of the diatom's frustule structure using Scanning electron microscopy (SEM) indicated that the presence of pore structures constitutes a pathway allowing MWCNTs uptake. The presence in the diatom's cytoplasm of MWCNTs might possibly induce disturbances of the cellular components, leading to the observed genotoxic and teratogenic effects. In view of previous studies, this work underscores the need for further studies on the interaction between nanomaterials and different diatom species, given the species-specific nature of the interactions.

Skin electroporation for transdermal drug delivery: Electrical measurements, numerical model and molecule delivery.

Skin electroporation for drug delivery involves the application of Pulsed Electric Fields (PEFs) on the skin to disrupt its barrier function in a temporary and non-invasive manner, increasing the uptake of drugs. It represents a potential alternative to delivery methods that are invasive (e.g. injections) or limited. We have developed a drug delivery system comprising nanocomposite hydrogels which act as a reservoir for the drug and an electrode for applying electric pulses on the skin. In this study, we employed a multi-scale approach to investigate the drug delivery system on a mouse skin model, through electrical measurements, numerical modeling and fluorescence microscopy. The Electrical properties indicated a highly non-linear skin conductivity behavior and were used to fine-tune the simulations and study skin recovery after electroporation. Simulation of electric field distribution in the skin showed amplitudes in the range of reversible tissue electroporation (400-1200 V/cm), for 300 V PEF. Fluorescence microscopy revealed increased uptake of fluorescent molecules compared to the non-pulsed control. We reported two reversible electroporation domains for our configuration: (1) at 100 V PEF the first local transport regions appear in the extracellular lipids of the stratum corneum, demonstrated by a rapid increase in the skin's conductivity and an increased uptake of lucifer yellow, a small hydrophilic fluorophore and (2) at 300 V PEF, the first permeabilization of nucleated cells occurred, evidenced by the increased fluorescence of propidium iodide, a membrane-impermeable, DNA intercalating agent.

Testing the Aquatic Toxicity of 2D Few-Layer Graphene Inks Using Rainbow Trout (Oncorhynchus mykiss): In Vivo and In Vitro Approaches to Support an SSbD Assessment.

Graphene-based conductive inks offer attractive possibilities in many printing technology applications. Often, these inks contain a mixture of compounds, such as solvents and stabilizers. For the safe(r) and sustainable use of such materials in products, potentially hazardous components must be identified and considered in the design stage. In this study, the hazards of few-layer graphene (FLG)-based ink formulations were tested in fish using in vitro (RTL-W1 cell line) and in vivo aquatic ecotoxicity tests (OECD TG 203). Five ink formulations were produced using different processing steps, containing varying amounts of solvents and stabilizers, with the end products formulated either in aqueous solutions or in powder form. The FLG ink formulations with the highest contents of the stabilizer sodium deoxycholate showed greater in vitro cytotoxic effects, but they did not provoke mortality in juvenile rainbow trout. However, exposure led to increased activities of the cytochrome P450 1a (Cyp1a) and Cyp3a enzymes in the liver, which play an essential role in the detoxification of xenobiotics, suggesting that any effects will be enhanced by the presence of the stabilizers. These results highlight the importance of an SSbD approach together with the use of appropriate testing tools and strategies. By incorporating additional processing steps to remove identified cytotoxic residual solvents and stabilizers, the hazard profile of the FLG inks improved, demonstrating that, by following the principles of the European Commission's safe(r) and sustainable by design (SSbD) framework, one can contribute to the safe(r) and sustainable use of functional and advanced 2D materials in products.

Analysis of carbon nanotube levels in organic matter: an inter-laboratory comparison to determine best practice.

Carbon nanotubes (CNTs) are increasingly being used in industrial applications, but their toxicological data in animals and humans are still sparse. To assess the toxicological dose-response of CNTs and to evaluate their pulmonary biopersistence, their quantification in tissues, especially lungs, is crucial. There are currently no reference methods or reference materials for low levels of CNTs in organic matter. Among existing analytical methods, few have been fully and properly validated. To remedy this, we undertook an inter-laboratory comparison on samples of freeze-dried pig lung, ground and doped with CNTs. Eight laboratories were enrolled to analyze 3 types of CNTs at 2 concentration levels each in this organic matrix. Associated with the different analysis techniques used (specific to each laboratory), sample preparation may or may not have involved prior digestion of the matrix, depending on the analysis technique and the material being analyzed. Overall, even challenging, laboratories' ability to quantify CNT levels in organic matter is demonstrated. However, CNT quantification is often overestimated. Trueness analysis identified effective methods, but systematic errors persisted for some. Choosing the assigned value proved complex. Indirect analysis methods, despite added steps, outperform direct methods. The study emphasizes the need for reference materials, enhanced precision, and organized comparisons.

Environmental and Health Impacts of Graphene and Other Two-Dimensional Materials: A Graphene Flagship Perspective.

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.

Carbon Nanotubes for Confinement-Induced Energetic Nanomaterials.

Oxidized carbon nanotubes obtained by catalytic chemical vapor deposition were filled with an aqueous solution of nano-energetic materials using a very simple impregnation method. The work compares different energetic materials but focuses especially on an inorganic compound belonging to the Werner complexes, [Co(NH3)6][NO3]3. Our results show a large increase in released energy upon heating, which we demonstrate to be related to the confinement of the nano-energetic material either directly by filling of the inner channel of carbon nanotubes or to insertion in the triangular channels between adjacent nanotubes when they form bundles.

Hydrogels from a Self-Assembling Tripeptide and Carbon Nanotubes (CNTs): Comparison between Single-Walled and Double-Walled CNTs.

Supramolecular hydrogels obtained from the self-organization of simple peptides, such as tripeptides, are attractive soft materials. Their viscoelastic properties can be enhanced through the inclusion of carbon nanomaterials (CNMs), although their presence can also hinder self-assembly, thus requiring investigation of the compatibility of CNMs with peptide supramolecular organization. In this work, we compared single-walled carbon nanotubes (SWCNTs) and double-walled carbon nanotubes (DWCNTs) as nanostructured additives for a tripeptide hydrogel, revealing superior performance by the latter. Several spectroscopic techniques, as well as thermogravimetric analyses, microscopy, and rheology data, provide details to elucidate the structure and behavior of nanocomposite hydrogels of this kind.