Nitrogen plasma modification boosts up the hemocompatibility of new PVDF-carbon nanohorns composite materials with potential cardiological and circulatory system implants application.

To design new material for blood-related applications one needs to consider various factors such as cytotoxicity, platelet adhesion, or anti-thrombogenic properties. The aim of this work is the design of new, highly effective materials possessing high blood compatibility. To do this, the new composites based on the poly(vinylidene fluoride) (PVDF) support covered with a single-walled carbon nanohorns (CNHs) layer were prepared. The PVDF-CNHs composites were subsequently used for the first time in the hemocompatibility studies. To raise the hemocompatibility a new, never applied before for CNHs, plasma-surface modifications in air, nitrogen and ammonia were implemented. This relatively cheap, facile and easy method allows generating the new hybrid materials with high effectiveness and significant differences in surface properties (water contact angle, surface ζ-potential, and surface functional groups composition). Changing those properties made it possible to select the most promising samples for blood-related applications. This was done in a fully controlled way by applying Taguchi's "orthogonal array" procedure. It is shown for the first time that nitrogen plasma treatment of new surfaces is the best tool for hemocompatibility rise and leads to very low blood platelet adhesion, no cytotoxicity, and excellent performance in thromboelastometry and hemolysis tests. We propose a possible mechanism explaining this behavior. The optimisation results are coherent with biological characterisation and are supported with Hansen Solubility Parameters. New surfaces can find potential applications in cardiological and circulatory system implants as well as other blood-related biomaterials.

Biomimetically Inspired Highly Homogeneous Hydrophilization of Graphene with Poly(l-DOPA): Toward Electroconductive Coatings from Water-Processable Paints.

Water-based processing of graphene-typically considered as physicochemically incompatible with water in the macroscale-emerges as the key challenge among the central postulates of green nanotechnology. These problematic concerns are derived from the complex nature of graphene in the family of sp2-carbon nanoallotropes. Indeed, nanomaterials hidden under the common "graphene" signboard are very rich in morphological and physicochemical variants. In this work, inspired by the adhesion chemistry of mussel biomaterials, we have synthesized novel, water-processable graphene-polylevodopa (PDOPA) hybrids. Graphene and PDOPA were covalently amalgamated via the "growth-from" polymerization of l-DOPA (l-3,4-dihydroxyphenylalanine) monomer in air, yielding homogeneously PDOPA-coated (23 wt %) (of thickness 10-20 nm) hydrophilic flakes. The hybrids formed >1 year stable and water-processable aqueous dispersions and further conveniently processable paints of viscosity 0.4 Pa·s at 20 s-1 and a low yield stress τ0 up to 0.12 Pa, hence exhibiting long shelf-life stability and lacking sagging after application. Demonstrating their applicability, we have found them as surfactant-like nanoparticles stabilizing the larger, pristine graphene agglomerates in water in the optimized graphene/graphene-PDOPA weight ratio of 9:1. These characteristics enabled the manufacture of conveniently paintable coatings of low surface resistivity of 1.9 kΩ sq-1 (0.21 Ω·m) which, in turn, emerge as potentially applicable in textronics, radar-absorbing materials, or electromagnetic interference shielding.

Linking the Defective Structure of Boron-Doped Carbon Nano-Onions with Their Catalytic Properties: Experimental and Theoretical Studies.

Defects are widely present in nanomaterials, and they are recognized as the active sites that tune surface properties in the local region for catalysis. Recently, the theory linking defect structures and catalytic properties of nanocatalysts has been most commonly described. In this study, we prepared boron-doped carbon nano-onions (B-CNOs) by applying an annealing treatment of ultradispersed nanodiamond particles and amorphous boron. These experimental conditions guarantee doping of CNOs with boron atoms in the entire carbon nanostructure, thereby ensuring structural homogeneity. In our research, we discuss the correlations between defective structures of B-CNOs with their catalytic properties toward SO2 and tert-butanol dehydration. We show that there is a close relationship between the catalytic properties of the B-CNOs and the experimental conditions for their formation. It is not only the mass of the substrates used for the formation of B-CNOs that is crucial, that is, the mass ratio of NDs to amorphous B, but also the process, including temperature and gas atmosphere. As it was expected, all B-CNOs demonstrated significant catalytic activity in HSO3- oxidation. However, the subsequent annealing in an air atmosphere diminished their catalytic activity. Unfortunately, no direct relationship between the catalytic activity and the presence of heteroatoms on the B-CNO surface was observed. There was a linear dependence between catalytic activity and Raman reactivity factors for each of the B-CNO materials. In contrast to SO2 oxidation, the B-CNO-a samples showed higher catalytic activity in tert-butanol dehydration due to the presence of Brønsted and Lewis acid sites. The occurence of three types of boron-Lewis sites differing in electron donor properties was confirmed using quantitative infrared spectroscopic measurements of pyridine adsorption.

Insight into the Mechanisms of Low Coverage Adsorption of N-Alcohols on Single Walled Carbon Nanohorn.

We report for the first time the chromatographic study of n-alcohols (from methanol to butanol) adsorption on single walled carbon nanohorn (SWCNH). Using measured temperature dependence of adsorption isotherms (373-433 K) the isosteric adsorption enthalpy is calculated and compared with the data reported for a graphite surface. It is concluded that a graphite surface is more homogeneous, and the enthalpy of adsorption on SWCNHs at zero coverage correlates well with molecular diameter and polarizability, suggesting leading role of dispersive interactions, i.e., no heteroatoms presence in the walls of SWCNH structures. Next using modern DFT approach we calculate the energy of n-alcohols interactions with a graphene sheet and with a single nanocone finally proposing a more realistic-double nanocone model. Obtained results suggest alcohols entrapping between SWCNH with OH groups located toward nanocones ends, leading to the conclusions about very promising future applications of SWCNHs in catalytic reactions with participation of n-alcohols.

Nitric-Acid Oxidized Single-Walled Carbon Nanohorns as a Potential Material for Bio-Applications-Toxicity and Hemocompatibility Studies.

The results of in vitro studies of single-walled carbon nanohorn (SWCNH) oxidized materials' cytotoxicity obtained by the cell membrane integrity (Neutral Red Uptake (NRU)) and metabolic activity (by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT)) on A549 and human dermal fibroblasts (HDF) cell lines are presented. We also present hemocompatibility studies on human and porcine blood, and an erythrocyte concentrate to prove that the obtained samples will not interfere with blood components. Characterization of the materials is supplemented by ζ-potential measurements, Transmission Electron Microscope (TEM) imaging, and thermogravimetric studies (TG). The presented results show the correlation between the specific surface area of materials and the platelet aggregation, when the ID/IG ratio determined from Raman spectra correlates with hemoglobin release from the erythrocytes (in whole blood testing). A plausible mechanism explaining the observed correlations is given. The cytotoxicity and hemocompatibility studies prove that the studied materials are acceptable for use in biomedical applications, especially a sample SWCNH-ox-1.5 with the best application potential.

Electrophoretic Deposition of Layer-by-Layer Unsheathed Carbon Nanotubes-A Step Towards Steerable Surface Roughness and Wettability.

It is well known that carbon nanotube (CNT) oxidation (usually with concentrated HNO3) is a major step before the electrophoretic deposition (EPD). However, the recent discovery of the "onion effect" proves that multiwalled carbon nanotubes are not only oxidized, but a simultaneous unsheathing process occurs. We present the first report concerning the influence of unsheathing on the properties of the thus-formed CNT surface layer. In our study we examine how the process of gradual oxidation/unsheathing of a series of multiwalled carbon nanotubes (MWCNTs) influences the morphology of the surface formed via EPD. Taking a series of well-characterized and gradually oxidized/unsheathing Nanocyl MWCNTs and performing EPD on a carbon fiber surface, we analyzed the morphology and wettability of the CNT surfaces. Our results show that the water contact angle could be gradually changed in a wide range (125-163°) and the major property determining its value was the diameter of aggregates formed before the deposition process in the solvent. Based on the obtained results we determined the parameters having a crucial influence on the morphology of created layers. Our results shed new light on the deposition mechanism and enable the preparation of surfaces with steerable roughness and wettability.