Different Classes Of Nanomaterials Research Articles

In English

Development of theoretical tools to analyze electronic structure of complex nanomaterials depending on features of spatial and chemical organizations of different phases is of interest from both practical and theoretical points of view. Therefore, in this work, an approach based on computations of the atomic charge distribution functions (CDF) in parallel to calculations of the distribution functions of the chemical shifts (SDF) of protons is developed to be applied to a set of complex oxide and carbon nanomaterials. Binary nanooxides (alumina/silica, titania/silica), 3d-metal-doped anatase, activated carbon, carbon nanotube, fullerene C60, graphene oxide, and N-doped Kagome graphene are considered here as representatives of different classes of nanomaterials. The analyses of the CDF and SDF as nonlocal characteristics of certain kinds of atoms in complex systems provide a deeper insight into electronic structure features depending on composition of the materials, guest phase-doped host phase at various amounts of dopants, structure of O- and OH-containing surface sites, amounts and organization of adsorbed water, formation of neutral and charged surface functionalities, bonding of solvated ions, etc. The CDF of metal and hydrogen atoms (electron-donors) are more sensitive to the mentioned factors than the CDF of O, N, and C atoms (electron acceptors) in various systems. As a whole, the use of the CDF and SDF in parallel expands the tool possibility in detailed analysis of the structural and interfacial effects in dried and wetted complex nanomaterials.

Machine-Learning-Based Approach to Decode the Influence of Nanomaterial Properties on Their Interaction with Cells

In an in vitro nanotoxicity system, cell-nanoparticle (NP) interaction leads to the surface adsorption, uptake, and changes into nuclei/cell phenotype and chemistry, as an indicator of oxidative stress, genotoxicity, and carcinogenicity. Different types of nanomaterials and their chemical composition or "corona" have been widely studied in context with nanotoxicology. However, rare reports are available, which delineate the details of the cell shape index (CSI) and nuclear area factors (NAFs) as a descriptor of the type of nanomaterials. In this paper, we propose a machine-learning-based graph modeling and correlation-establishing approach using tight junction protein ZO-1-mediated alteration in the cell/nuclei phenotype to quantify and propose it as indices of cell-NP interactions. We believe that the phenotypic variation (CSI and NAF) in the epithelial cell is governed by the physicochemical descriptors (e.g., shape, size, zeta potential, concentration, diffusion coefficients, polydispersity, and so on) of the different classes of nanomaterials, which critically determines the intracellular uptake or cell membrane interactions when exposed to the epithelial cells at sub-lethal concentrations. The intrinsic and extrinsic physicochemical properties of the representative nanomaterials (NMs) were measured using optical (dynamic light scattering, NP tracking analysis) methods to create a set of nanodescriptors contributing to cell-NM interactions via phenotype adjustments. We used correlation function as a machine-learning algorithm to successfully predict cell and nuclei shapes and polarity functions as phenotypic markers for five different classes of nanomaterials studied herein this report. The CSI and NAF as nanodescriptors can be used as intuitive cell phenotypic parameters to define the safety of nanomaterials extensively used in consumer products and nanomedicine.

Nanomaterials: Classification, properties, and environmental toxicities

Nanomaterials (NMs) are gaining significance in technological applications due to their tunable chemical, physical, and mechanical properties and enhanced performance when compared with their bulkier counterparts. This review presents a summary of the general types of NMs and provides an overview of the various synthesis methods of nanoparticles (NPs) and their functionalization via covalent or noncovalent interactions using different methods. It highlights the techniques used for the characterization of NPs and discusses their physical and chemical properties. Due to their unique properties, NMs have several applications and have become part of our daily lives. As a result, nanotoxicity research is gaining attention since some NPs are not easily degraded by the environment. Thus, this review also highlights research efforts into the fate, behavior, and toxicity of different classes of NMs in the environment.

Iron Strapped Porphyrins on Carbon Nanotubes As Hybrid Materials for the ORR Reaction

One of the most important challenge of nanosciences is the fabrication of functional hybrid materials, preserving and combining the properties of their building blocks. Among the different classes of nanomaterials, carbon nanotubes are promising for electronics, opto-electronics, catalysis and composite applications. Within the context of sustainable development and renewable energy, we and others have been envisioning the use of functionalized or doped carbon nanotubes in electrocatalytic systems.1,2 In such systems, catalytic sites need to be supported on conducting materials. Carbon nanotubes, thanks to their electrical conductivity and their high surface, area appear to be the ideal material for that purpose.In actual Proton Exchange Membrane Fuel Cell Devices (PEMFC), the reactions at the electrodes and in particular the reduction of oxygen are performed by platinum nanoparticles. The cost of platinum is an incentive to developing new catalysts-based on non-noble metals. Thus, whereas in nature oxygen reduction is performed by iron porphyrins in the active center of enzymes, bio-inspired catalysts based on cobalt or iron macrocycles have been extensively studied for Oxygen Reduction Reaction (ORR).3,4 Here, we describe the synergic effect on catalytic activity of carbon nanotubes and strapped iron porphyrin hybrids for ORR. In particular, we demonstrate that combining both MWNTs and porphyrins leads to better catalytic activity compared to isolated nanotubes or porphyrins on their own. This study hence highlights the importance of carbon support for the catalysis: nanotubes ensure the availability of electrons to porphyrin catalysts and allow ORR to occur via the 4-electron pathway, avoiding the production of hydrogen peroxide.For this study, two series of iron-strapped porphyrins have been explored.5-6 In the first one, the porphyrins were adsorbed at the surface on nanotubes whereas, for the second one, porphyrins were synthesized with propargylic ether groups at their periphery, allowing covalent linkage by Hay coupling at the surface of the nanotubes. Each of the nanotube hybrids was characterized and tested for ORR in a series of electrochemical measurements.

The Renaissance of Luminescent Solar Concentrators: The Role of Inorganic Nanomaterials

AbstractWhile luminescent solar concentrators (LSCs) have a simple architecture—a transparent matrix embedding a luminescent fluorophore coupled with solar cells at the lateral side of the LSC slab—multiple paths for possible light losses exist. These are inherently interconnected, and in the past, limited the interest in this device, due to the gap between the theoretical possibilities and experimental achievements. This gap was a result, primarily, of the optical features of the luminescent dyes, since conventional organic luminophores are affected by limited performance in LSC devices. The rise of a wide portfolio of optically active inorganic nanomaterials in the last decade provides an alternative to organic dyes and has lead to a renaissance in the role of LSCs among the unconventional solar energy conversion devices. This paper reviews the latest results in the development of LSCs based on different classes of nanomaterials, focusing on the specific features and critically analyzing the pros and cons of the proposed structures. Particular attention is devoted to the role of the luminescence properties, e.g., the Stokes shift and the photoluminescence quantum yield, with respect to the performance of the LSC device. Future challenges to the successful employment of these devices for building integrated photovoltaics are also discussed.

Simultaneous transcriptome and proteome analysis of EA.hy926 cells under stress conditions induced by nanomaterials.

Today, the extensive and constantly growing number of applications in the field of nanotechnology poses a lot of questions about the potential toxicity of nanomaterials (NMs) toward cells of different origins. In our work we employed the tools of molecular biology to evaluate changes that occur in human endothelial cells at the transcriptomic and proteomic level, following 24 h of exposure to three different classes of NMs. Using microarray technology, we demonstrated that 24 h of exposure to silver nanoparticles (SNPs), multiwalled carbon nanotubes (MWCNTs) and polyamidoamine dendrimers (PAMAMs) leads to changes in 299, 1271, and 431 genes, respectively, influencing specific molecular pathways. The 2D-DIGE and mass spectrometry analysis revealed that differentially expressed proteins were involved in numerous cellular processes, for example, cytoskeletal reorganization, cell growth and proliferation, or response to stress. Both, transcriptome and proteome alterations indicate reorganization of mechanism regulating cell functioning. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 107B: 1024-1034, 2019.

The Many "Facets" of Halide Ions in the Chemistry of Colloidal Inorganic Nanocrystals.

Over the years, scientists have identified various synthetic “handles” while developing wet chemical protocols for achieving a high level of shape and compositional complexity in colloidal nanomaterials. Halide ions have emerged as one such handle which serve as important surface active species that regulate nanocrystal (NC) growth and concomitant physicochemical properties. Halide ions affect the NC growth kinetics through several means, including selective binding on crystal facets, complexation with the precursors, and oxidative etching. On the other hand, their presence on the surfaces of semiconducting NCs stimulates interesting changes in the intrinsic electronic structure and interparticle communication in the NC solids eventually assembled from them. Then again, halide ions also induce optoelectronic tunability in NCs where they form part of the core, through sheer composition variation. In this review, we describe these roles of halide ions in the growth of nanostructures and the physical changes introduced by them and thereafter demonstrate the commonality of these effects across different classes of nanomaterials.

(Invited) Carbon Nanotube and Porphyrins: Materials for Optics and Energy Applications

The fabrication of functional hybrid materials that preserves and combines the properties of their building blocks is a central issue of nanosciences. Among the different classes of nanomaterials, carbon nanotubes are promising for electronics, opto-electronics, catalysis and composite applications. In this context the combination of nanotubes with porphyrins has been widely explored for catalytic1,2 or electron transfer purposes.3,4 Here I present two results obtained recently on the nanotube/porphyrin composites, the first deals with the supramolecular organization in micelles of porphyrins around the nanotubes.5 In this work we were able to explain the Davidoff splitting observed on the absorption bands of the porphyrins by their organization around the nanotubes. The second deals with the synergic effect on catalytic activity of carbon nanotubes and strapped iron porphyrin hybrids for Oxygen Reduction Reaction (ORR).6 In particular, we demonstrated that the combination of both components - MWNTs and porphyrin - leads to a better catalytic activity than those of the nanotubes or the porphyrins taken separately. This study highlights the importance of the carbon support for the catalysis. The nanotubes ensure the availability of electrons to the porphyrin catalysts and allow the ORR to occur via the 4-electron pathway, avoiding the production of hydrogen peroxide. Reference List: (1) McGuire Jr, R.; Dogutan, D. K.; Teets, T. S.; Suntivich, J.; Shao-Horn, Y.; Nocera, D. G. Chem. Sci. 2010, 1, 411-414. (2) Hijazi, I.; Bourgeteau, T.; Cornut, R.; Morozan, A.; Filoramo, A.; Leroy, J.; Derycke, V.; Jousselme, B.; Campidelli, S. J. Am. Chem. Soc. 2014, 136, 6348-6354. (3) Umeyama, T.; Imahori, H. J. Phys. Chem. C 2013, 117, 3195-3209. (4) Dirian, K.; Herranz, M. A.; Katsukis, G.; Malig, J.; Rodríguez-Pérez, L.; Romero-Nieto, C.; Strauss, V.; Martín, N.; Guldi, D. M. Chem. Sci. 2013, 4, 4335-4353. (5) Delport, G.; Vialla, F.; Roquelet, C.; Campidelli, S.; Voisin, C.; Lauret, J.-S. Nano Lett. 2017, 17, 6778-6782. (6) Hanana, M.; Arcostanzo, H.; Bouget, M.; Das, P. K.; Le Gac, S.; Cornut, R.; Jousselme, B.; Boitrel, B.; Campidelli, S. submitted.

(Invited) Carbon Nanotube-Templated Synthesis of Covalent Porphyrin Network for Oxygen Reduction Reaction

The fabrication of functional hybrid materials that preserves and combines the properties of their building blocks is a central issue of nanosciences. Among the different classes of nanomaterials, carbon nanotubes are promising for electronics, catalysis and composite applications. Within the context of sustainable development and renewable energy, we and others envisioned the use of functionalized or doped carbon nanotubes in electrocatalytic systems.1 , 2 In such systems, the catalytic sites need to be supported on conducting materials. Carbon nanotubes, thanks to their electrical conductivity and their high surface area appear as the ideal material for that purpose. In actual proton exchange membrane fuel cell devices (PEMFC), the reactions at the electrodes and in particular the reduction of oxygen is performed by platinum nanoparticles. The cost of platinum encourages the development of new catalysts based on non-noble metals. In nature, the reduction of oxygen is performed by iron porphyrins in the active center of enzymes. Thus bio-inspired catalysts based on cobalt or iron macrocycles have been extensively studied for oxygen reduction reaction (ORR).3 , 4 Here, we describe the formation of a covalent network of porphyrins around MWNTs. Our approach is based on adsorption of ethynylporphyrins followed by the dimerization of the triple bonds. The nanotube acts as a template for the formation of the polymeric layer. The nanotube hybrids were characterized and tested for the ORR in a series of electrochemical measurements in acidic conditions. Compared to similar systems in which monomeric porphyrins are simply physisorbed, the nanotube hybrib showed a higher activity, a higher current density, a lower overpotential and a four electrons reaction pathway.5 References (1) Zhang, W.; Sherrell, P.; Minett, A. I.; Razal, J. M.; Chen, J. Energy Environ. Sci. 2010, 3, 1286-1293. (2) Morozan, A.; Jousselme, B.; Palacin, S. Energy Environ. Sci. 2011, 4, 1238-1254. (3) Zagal, J. H.; Griveau, S.; Silva, J. F.; Nyokong, T.; Bedioui, F. Coord. Chem. Rev. 2010, 254, 2755-2791. (4) Morozan, A.; Campidelli, S.; Filoramo, A.; Jousselme, B.; Palacin, S. Carbon 2011, 49, 4839-4847. (5) Hijazi, I.; Bourgeteau, T.; Cornut, R.; Morozan, A.; Filoramo, A.; Leroy, J.; Derycke, V.; Jousselme, B.; Campidelli, S. J. Am. Chem. Soc. 2014, 136, 6348-6354. Figure 1

Autophagy as a Possible Underlying Mechanism of Nanomaterial Toxicity.

The rapid development of nanotechnologies is raising safety concerns because of the potential effects of engineered nanomaterials on human health, particularly at the respiratory level. Since the last decades, many in vivo studies have been interested in the pulmonary effects of different classes of nanomaterials. It has been shown that some of them can induce toxic effects, essentially depending on their physico-chemical characteristics, but other studies did not identify such effects. Inflammation and oxidative stress are currently the two main mechanisms described to explain the observed toxicity. However, the exact underlying mechanism(s) still remain(s) unknown and autophagy could represent an interesting candidate. Autophagy is a physiological process in which cytoplasmic components are digested via a lysosomal pathway. It has been shown that autophagy is involved in the pathogenesis and the progression of human diseases, and is able to modulate the oxidative stress and pro-inflammatory responses. A growing amount of literature suggests that a link between nanomaterial toxicity and autophagy impairment could exist. In this review, we will first summarize what is known about the respiratory effects of nanomaterials and we will then discuss the possible involvement of autophagy in this toxicity. This review should help understand why autophagy impairment could be taken as a promising candidate to fully understand nanomaterials toxicity.

Efficient covalent functionalisation of carbon nanotubes: the use of “click chemistry”

Amongst the different classes of nanomaterials, carbon nanotubes (CNTs) are extremely promising for applications in electronics, solar energy conversion, materials science and medicinal chemistry. However in order to use them for those applications an accurate control of the functionalisation of the nanotubes is required. Many reactions can be performed on the π-conjugated framework of CNTs (i.e. cycloadditions, radical additions or halogenations). These reactions, although very efficient, require, in general, experimental conditions which are weakly compatible with sensitive organic or biological compounds. The emergence of new or re-actualised synthetic methods (known under the term of “click chemistry”) has the potential to provide an elegant protocol to prepare carbon nanotube-based functional materials. This review will gather the recent results described in the literature using “click chemistry” to functionalise carbon nanotubes.

Toxicity and Environmental Risks of Nanomaterials: Challenges and Future Needs

Nanotechnology has gained a great deal of public interest because of the needs and applications of nanomaterials in many areas of human endeavors including industry, agriculture, business, medicine, and public health. Environmental exposure to nanomaterials is inevitable as nanomaterials become part of our daily life, and, as a result, nanotoxicity research is gaining attention. This review presents a summary of recent research efforts on fate, behavior, and toxicity of different classes of nanomaterials in the environment. A critical evaluation of challenges and future needs for the safe environmental nanotechnology are discussed.

NANOMATERIALS AS OPTICAL LIMITERS

Optical limiters based on several different classes of nanomaterials are reviewed. The systems under consideration include metal and semiconductor nanoparticles and nanoscale carbon materials. For the latter, the optical limiting properties of carbon nanoparticles, fullerenes, and suspended and solubilized carbon nanotubes are summarized and compared. Mechanistic implications of the available experimental results are discussed in terms of the comparison between nonlinear scattering versus nonlinear absorption as the dominating optical limiting mechanism for different nanomaterials and for different physico-chemical states of a nanomaterial.