RESUMEN
Interactions of graphene oxide (GO) with an ex vivo rat heart and its coronary vessels have not been studied yet. Moreover, the conflicting data on the "structure-properties" relationships do not allow for biomedical applications of GO. Herein, we study the impact of GO on the ex vivo isolated rat heart, normotensive and hypertensive, under the working heart and the constant-pressure perfusion (Langendorff) regimes. Four structural GO variants of the following initial morphology were used: few-layer (below 10-layer) GO1, O < 49%; predominantly single-layer GO2, O = 41-50%; 15-20-layer GO3, O < 11%; and few-layer (below 10-layer) NH4 +-functionalized GO4, O < 44%, N = 3-6%. The aqueous GO dispersions, sonicated and stabilized with bovine serum albumin in Krebs-Henseleit-like solution-uniformized in terms of the particle size-were eventually size-monodisperse as revealed by dynamic light scattering. To study the cardiotoxicity mechanisms of GO, histopathology, Raman spectroscopy, analysis of cardiac parameters (coronary and aortic flows, heart rate, aortic pressure), and nitric oxide (NO-)-dependent coronary flow response to bradykinin (blood-vessel-vasodilator) were used. GO1 (10 mg/L) exerted no effects on cardiac function and preserved an increase in coronary flow in response to bradykinin. GO2 (10 mg/L) reduced coronary flow, aortic pressure in normotensive hearts, and coronary flow in hypertensive hearts, and intensified the response to bradykinin in normal hearts. GO3 (10 mg/L) reduced all parameters in hypertensive hearts and coronary response to bradykinin in normal hearts. At higher concentrations (normotensive hearts, 30 mg/L), the coronary response to bradykinin was blocked. GO4 (10 mg/L) reduced the coronary flow in normal hearts, while for hypertensive hearts, all parameters, except the coronary flow, were reduced and the coronary response to bradykinin was blocked. The results showed that a low number of GO layers and high O-content were safer for normal and hypertensive rat hearts. Hypertensive hearts deteriorated easier upon perfusion with low-O-content GOs. Our findings support the necessity of strict control over the GO structure during organ perfusion and indicate the urgent need for personalized medicine in biomedical applications of GO.
RESUMEN
The need to identify secondary sources of REEs and their recovery has led to the search for new methods and materials. In this study, a novel type of ion-imprinted adsorption membranes based on modified chitosan was synthesized. Their application for the recovery of chosen REEs from synthetic coal fly ash extracts was analyzed. The examined membranes were analyzed in terms of adsorption kinetics, isotherms, selectivity, reuse, and their separation abilities. The experimental data obtained were analyzed with two applications, namely, REE 2.0 and REE_isotherm. It was found that the adsorption of Nd3+ and Y3+ ions in the obtained membranes took place according to the chemisorption mechanism and was significantly controlled by film diffusion. The binding sites on the adsorbent surface were uniformly distributed; the examined ions showed the features of regular monolayer adsorption; and the adsorbents showed a strong affinity to the REE ions. The high values of Kd (900-1472.8 mL/g) demonstrate their high efficiency in the recovery of REEs. After five subsequent adsorption-desorption processes, approximately 85% of the value of one cycle was reached. The synthesized membranes showed a high rejection of the matrix components (Na, Mg, Ca, Al, Fe, and Si) in the extracts of the coal fly ashes, and the retention ratio for these Nd and Y ions was 90.11% and 80.95%, respectively.
RESUMEN
Carbon nanoallotropes have attracted significant attention in the field of materials science due to their unique combination of physicochemical and biological properties, with numerous applications. One-dimensional (1D) and two-dimensional (2D) sp2-carbon nanoallotropes, such as carbon nanohorns (CNHs), carbon nanotubes (CNTs), and graphene, have emerged as prominent candidates for a variety of technological advancements. To fully exploit their exceptional characteristics, the covalent functionalization of these nanostructures may alleviate the problems with the processing and final performance. This route of the carbon nanoallotrope functionalization is based on a covalent attachment of functional groups or molecules (via linkers of various strengths) to their surfaces, enabling precise control over physical, chemical, biological, and electronic properties. Such an approach opens up new avenues for tailoring the nanoallotrope characteristics, such as solubility/dispersibility, reactivity, and interactions with other materials. Over more than the last decade, significant progress has been made in the covalent functionalization of both 1D and 2D sp2-carbon nanoallotropes, paving the way for diverse applications in the nanoelectronics, energy storage, sensing, and biomedical fields. In this comprehensive review, we provide state-of-the-art advancements and achievements in the covalent functionalization of 1D and 2D sp2-carbon nanoallotropes during the past dozen years. We aim to highlight the key strategies, methodologies, and breakthroughs that have significantly contributed to this field. Eventually, we discuss the implications of those advancements and explore the opportunities for future research and applications.
RESUMEN
The design of shielding materials against ionizing radiation while simultaneously displaying enhanced multifunctional characteristics remains challenging. Here, for the first time, we present moldable paraffin-based iron nano- and microcomposites attenuating γ- and X-radiation. The moldability was gained by the warmth-of-hands-driven plasticity, which allowed for obtaining a specific shape of the composites at room temperature. The manufactured composites contained iron particles of various sizes, ranging from 22 nm to 63 µm. The target materials were widely characterized using XRD, NMR, Raman, TGA, SEM, and EDX. In the case of microcomposites, the shielding properties were developed at two concentrations: 10 and 50 wt %. The statistically significant results indicate that the iron particle size has a negligible effect on the shielding properties of the nano- and microcomposites. On the other hand, the higher iron particle contents significantly affected the attenuating ability, which emerged even as superior to the elemental aluminum in the X-ray range: at a 70 kV anode voltage, the half value layer was 6.689, 1.882, and 0.462 cm for aluminum, paraffin + 10 wt % Fe 3.5-6.5 µm, and paraffin + 50 wt % Fe 3.5-6.5 µm microcomposites, respectively. Importantly, the elaborated methodology-in situ cross-verified in the hospital studies recording real-life sampling-opens the pathway to high-performance, eco-friendly, lightweight, and recyclable shields manufactured via fully reproducible and scalable protocols.
RESUMEN
Graphene oxide's (GO) intravascular applications and biocompatibility are not fully explored yet, although it has been proposed as an anticancer drug transporter, antibacterial factor or component of wearable devices. Bivalent cations and the number of particles' atom layers, as well as their structural oxygen content and pH of the dispersion, all affect the GO size, shape, dispersibility and biological effects. Bovine serum albumin (BSA), an important blood plasma protein, is expected to improve GO dispersion stability in physiological concentrations of the precipitating calcium and magnesium cations to enable effective and safe tissue perfusion. METHODS: Four types of GO commercially available aqueous dispersions (with different particle structures) were diluted, sonicated and studied in the presence of BSA and physiological cation concentrations. Nanoparticle populations sizes, electrical conductivity, zeta potential (Zetasizer NanoZS), structure (TEM and CryoTEM), functional groups content (micro titration) and dispersion pH were analyzed in consecutive preparation stages. RESULTS: BSA effectively prevented the aggregation of GO in precipitating concentrations of physiological bivalent cations. The final polydispersity indexes were reduced from 0.66-0.91 to 0.36-0.43. The GO-containing isotonic dispersions were stable with the following Z-ave results: GO1 421.1 nm, GO2 382.6 nm, GO3 440.2 nm and GO4 490.1 nm. The GO behavior was structure-dependent. CONCLUSION: BSA effectively stabilized four types of GO dispersions in an isotonic dispersion containing aggregating bivalent physiological cations.
RESUMEN
We present a novel external-catalyst-free route for the synthesis of N-doped carbon nanotubes (N-CNTs) from amino-acid-derived carbon dots (CDs) as sustainable resources. N-CNTs (â¼4-26 at% of N) were comprehensively characterized by complementary techniques while the synthetic strategy emerges as an important alternative and, simultaneously, a simply-scalable approach.
Asunto(s)
Nanotubos de Carbono , Puntos Cuánticos , CatálisisRESUMEN
A growing population suffering from or at high risk of developing cardiovascular diseases can benefit from rapid, precise, and readily available diagnostics. Textronics is an interdisciplinary approach for designing and manufacturing high-performance flexible electronics integrated with textiles for various applications, with electrocardiography (ECG) being the most convenient and most frequently used diagnostic technique for textronic solutions. The key challenges that still exist for textronics include expedient manufacturing, adaptation to human subjects, sustained operational stability for Holter-type data acquisition, reproducibility, and compatibility with existing solutions. The present study demonstrates conveniently paintable ECG electroconductive coatings on T-shirts woven from polyester or 70% polyamide and 30% polyester. The up to 600-µm-thick coatings encompass working electrodes of low resistivity 60 Ω sq-1 sheathed in the insulated pathways-conjugable with a wireless, multichannel ECG recorder. Long (800 µm) multiwalled carbon nanotubes, with scalable reproducibility and purity (18 g per round of synthesis), constituted the electroactive components and were embedded into a commercially available screen-printing acrylic base. The resulting paint had a viscosity of 0.75 Pa·s at 56 s-1 and 25 °C and was conveniently applied using a paintbrush, making this technique accessible to manufacturers. The amplified and nondigitally processed ECG signals were recorded under dry-skin conditions using a certified ECG recorder. The system enabled the collection of ECG signals from two channels, allowing the acquisition of cardiac electrical activity on six ECG leads with quality at par with medical diagnostics. Importantly, the Holter-type ECG allowed ambulatory recording for >24 h under various activities (sitting, sleeping, walking, and running) in three male participants. The ECG signal was stable for >5 cycles of washing, a level of stability not reported yet previously. The developed ECG-textronic application possesses acceptable and reproducible characteristics, making this technology a suitable candidate for further testing in clinical trials.
RESUMEN
Investments in the transfer and storage of thermal energy along with renewable energy sources strengthen health and economic infrastructure. These factors intensify energy diversification and the more rapid post-COVID recovery of economies. Ionanofluids (INFs) composed of long multiwalled carbon nanotubes (MWCNTs) rich in sp2-hybridized atoms and ionic liquids (ILs) display excellent thermal conductivity enhancement with respect to the pure IL, high thermal stability, and attractive rheology. However, the influence of the morphology, physicochemistry of nanoparticles and the IL-nanostructure interactions on the mechanism of heat transfer and rheological properties of INFs remain unidentified. Here, we show that intertube nanolayer coalescence, supported by 1D geometry assembly, leads to the subzipping of MWCNT bundles and formation of thermal bridges toward 3D networks in the whole INF volume. We identified stable networks of straight and bent MWCNTs separated by a layer of ions at the junctions. We found that the interactions between the ultrasonication-induced breaking nanotubes and the cations were covalent in nature. Furthermore, we found that the ionic layer imposed by close MWCNT surfaces favored enrichment of the cis conformer of the bis(trifluoromethylsulfonyl)imide anion. Our results demonstrate how the molecular perfection of the MWCNT structure with its supramolecular arrangement affects the extraordinary thermal conductivity enhancement of INFs. Thus, we gave the realistic description of the interactions at the IL-CNT interface with its (super)structure and chemistry as well as the molecular structure of the continuous phase. We anticipate our results to be a starting point for more complex studies on the supramolecular zipping mechanism. For example, ionically functionalized MWCNTs toward polyionic systemsâof projected and controlled nanolayersâcould enable the design of even more efficient heat-transfer fluids and miniaturization of flexible electronics.
RESUMEN
Carbon quantum dots (CQDs) were synthesized via a green, one-step hydrothermal method. As CQD precursors, nine amino acids of different structural descriptors (negatively/positively charged in water, polar, hydrophobic, sulfur-containing, and other/complex ones) were surveyed: Asp, Cys, Gly, His, Leu, Lys, Phe, Pro, and Ser. The reactions were performed in an autoclave in the presence of citric acid at 180 °C for 24 h and yielded core-shell CQDs. CQDs were comprehensively characterized by transmission electron microscopy, dynamic light scattering, Raman, UV/Vis, infrared, X-ray photoelectron spectroscopy, and fluorescence spectroscopy. At the excitation wavelength of λex = 350 nm, Cys-, Phe-, Leu-, and Lys-based CQDs displayed the highest quantum yield blue fluorescence-90 ± 5, 90 ± 4, 87 ± 5, and 67 ± 3%, respectively-superior to the conventional fluorescent dyes. Strikingly, for Lys- and Phe-CQDs, dissimilar trends in the excitation-emission wavelength relationships were identified, that is, constantly strong red shifts versus excitation wavelength-independent emission. Cys- and Lys-CQDs were water-dispersible toward the narrow unimodal distribution of hydrodynamic diameters-0.6 and 2.5 nm, respectively. Additionally, Lys- and Cys-CQDs, with high absolute zeta potential values, formed stable aqueous colloids in a broad range of pH (2, 7, and 12). The results constitute important premises for water-based applications of CQDs, such as bioimaging or photocatalysis.
RESUMEN
The need to reduce greenhouse gas emissions dictates the search for new methods and materials. Here, a novel type of inorganic-organic hybrid materials Fe@MWCNT-OH/SPEEK (with a new type of CNT characterized by increased iron content, 5.80 wt%) for CO2 separation is presented. The introduction of nanofillers into a polymer matrix has significantly improved hybrid membrane gas transport (D, P, S, and α CO2/N2 ), and magnetic, thermal, and mechanical parameters. It was found that magnetic casting has improved the alignment and dispersion of Fe@MWCNT-OH carbon nanotubes. At the same time, CNT and polymer chemical modification enhanced interphase compatibility and membrane CO2 separation efficiency. The thermooxidative stability, and mechanical and magnetic parameters of composites were improved by increasing new CNT loading. Cherazi's model turned out to be suitable for describing the CO2 transport through analyzed hybrid membranes. The comparison of the transport and separation properties of the tested membranes with the literature data indicates their potential application in the future and the direction of further research.
RESUMEN
Geopolymers, recognized as an ecological alternative to cement concrete, are gaining more and more interest from researchers and the construction industry. Due to the registrable electrical conductivity, this material also attracts the interest of other fields of science and industry as a potential functional material. The article discusses the used geopolymer material, created on the basis of metakaolin and waste Cathode Ray Tubes (CRT) glass, reinforced with ultra-long in-house carbon nanotubes (CNT), in the context of its use as a smart material for Structural Health Monitoring. Long in-house made carbon nanotubes were added to enhance the electrical conductivity of the geopolymer. The impedance spectroscopy method was applied to investigate the conductive properties of this material. The paper shows the microscopic and mechanical characteristics of the materials and presents the results of promising impedance spectroscopy tests.
RESUMEN
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.
RESUMEN
The fascinating tribological phenomenon of carbon nanotubes (CNTs) observed at the nanoscale was confirmed in our numerous macroscale experiments. We designed and employed CNT-containing nanolubricants strictly for polymer lubrication. In this paper, we present the experiment characterising how the CNT structure determines its lubricity on various types of polymers. There is a complex correlation between the microscopic and spectral properties of CNTs and the tribological parameters of the resulting lubricants. This confirms indirectly that the nature of the tribological mechanisms driven by the variety of CNT-polymer interactions might be far more complex than ever described before. We propose plasmonic interactions as an extension for existing models describing the tribological roles of nanomaterials. In the absence of quantitative microscopic calculations of tribological parameters, phenomenological strategies must be employed. One of the most powerful emerging numerical methods is machine learning (ML). Here, we propose to use this technique, in combination with molecular and supramolecular recognition, to understand the morphology and macro-assembly processing strategies for the targeted design of superlubricants.
RESUMEN
Novel inorganic-organic hybrid membranes Fe@MWCNT/PPO or Fe@MWCNT-OH/SPPO (with a new type of CNTs characterized by increased iron content 5.80 wt%) were synthesized for CO2 separation. The introduction of nanofillers into the polymer matrix has significantly improved the hybrid membrane's gas transport (D, P, S, and αCO2/N2), magnetic, thermal, and mechanical parameters. It was found that magnetic casting has improved the alignment and dispersion of Fe@MWCNTs. At the same time, CNTs and polymer chemical modification enhanced interphase compatibility and the membrane's CO2 separation efficiency. The thermo-oxidative stability and mechanical and magnetic parameters of composites were improved by increasing new CNTs loading. Cherazi's model turned out to be suitable for describing the CO2 transport through analyzed hybrid membranes.
RESUMEN
As a result of strict regulations of phthalate plasticizers, alternative non-phthalate forms are desired and increasingly used. This work presents a synthetic method for alternative plasticizers (dialkyl succinates and adipates) via esterification of succinic and adipic acid with alcohols: butan-1-ol and 2-ethylhexan-1-ol. Ionic liquids were synthesized by the reaction of triethylamine with over-equimolar (1:2.7) amounts of sulfuric(VI) acid, which were used as an acidic catalyst and solvent. The two-phase liquid-liquid system was formed during the reaction due to immiscibility of the esters with the ionic liquid. This phenomenon is a driving force of this process, shifting the equilibrium toward the product formation. As a result, dialkyl succinates and adipates were obtained in high yields (99%) and selectivities (>99%), under mild reaction conditions at 70-80 °C and using a 4:1 molar ratio of alcohol to acid and 15 mol% of catalyst. The catalyst was recycled 10 times without any loss of activity. This alternative method is highly competitive: it involves a simple procedure for product isolation as well as a high yield and purity of the resulting esters. These advantages make this method sustainable and promising for industrial applications.
RESUMEN
The stability along with thermal and rheological characteristics of ionanofluids (INFs) profoundly depend on the protocol of preparation. Therefore, in this work, the effect of ultrasonication time on microstructure, thermal conductivity, and viscosity of INFs containing 0.2 wt% of originally ultra-long multi-walled carbon nanotubes (MWCNTs) and four different ILs, namely 1-propyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1-ethyl-3-methylimidazolium thiocyanate, or 1-ethyl-3-methylimidazolium tricyanomethanide, was studied. The INFs were obtained by a two-step method using an ultrasonic probe. The ultrasonication process was performed for 1, 3, 10, or 30 min at a constant nominal power value of 200 W. The obtained results showed that for the shortest sonication time, the highest thermal conductivity enhancement of 12% was obtained. The extended sonication time from 1 to 30 min caused the cutting of MWCNTs and breaking the nanoparticle clusters, leading to a decrease in the average length of the nanotube bundles by approx. 70%. This resulted in a decline in thermal conductivity even by 7.2% and small deviations from the Newtonian behavior of INFs.
RESUMEN
HYPOTHESIS: Carbon nanotubes (CNTs) represent a novel platform for cellular delivery of therapeutic peptides. Chemically-functionalized CNTs may enhance peptide uptake by improving their membrane targeting properties. EXPERIMENTS: Using coarse-grained (CG) molecular dynamics (MD) simulations, we investigate membrane interactions of a peptide conjugated to pristine and chemically-modified CNTs. As proof of principle, we focus on their interactions with PM2, an amphipathic stapled peptide that inhibits the E3 ubiquitin ligase HDM2 from negatively regulating the p53 tumor suppressor. CNT interaction with both simple planar lipid bilayers as well as spherical lipid vesicles was studied, the latter as a surrogate for curved cellular membranes. FINDINGS: Membrane permeation was rapid and spontaneous for both pristine and oxidized CNTs when unconjugated. This was slowed upon addition of a noncovalently attached peptide surface "sheath", which may be an effective way to slow CNT entry and avert membrane rupture. The CNT conjugates were observed to "desheath" their peptide layer at the bilayer interface upon insertion, leaving their cargo behind in the outer leaflet. This suggests that a synergy may exist to optimize CNT safety whilst enhancing the delivery efficiency of "hitchhiking" therapeutic molecules.
Asunto(s)
Nanotubos de Carbono , Membrana Celular , Membrana Dobles de Lípidos , Simulación de Dinámica Molecular , PéptidosRESUMEN
A novel method for chemo-enzymatic Baeyer-Villiger oxidation of cyclic ketones in the presence of supported ionic liquid-like phase biocatalyst was designed. In this work, multi-walled carbon nanotubes were applied as a support for ionic liquids which were anchored to nanotubes covalently by amide or imine bonds. Next, lipases B from Candida antarctica, Candida rugosa, or Aspergillus oryzae were immobilized on the prepared materials. The biocatalysts were characterized using various techniques, like thermogravimetry, IR spectroscopy, XPS, elemental analysis, and SEM-EDS microscopy. In the proposed approach, a biocatalyst consisting of a lipase as an active phase allowed the generation of peracid in situ from the corresponding precursor and a green oxidant-hydrogen peroxide. The activity and stability of the obtained biocatalysts in the model oxidation of 2-adamantanone were demonstrated. High conversion of substrate (92%) was achieved under favorable conditions (toluene: n-octanoic acid ratio 1:1 = v:v, 35% aq. H2O2 2 eq., 0.080 g of biocatalyst per 1 mmol of ketone at 20 °C, reaction time 4 h) with four reaction cycles without a drop in its activity. Our 'properties-by-design' approach is distinguished by its short reaction time at low temperature and higher thermal stability in comparison with other biocatalysts presented in the literature reports.
RESUMEN
This study presents a highly efficient method of a synthesis of n-butyl acrylate via esterification of acrylic acid and n-butanol in the presence of supported ionic liquid phase (SILP) biocatalyst consisting of the lipase B from Candida antarctica (CALB) and multi-walled carbon nanotubes (MWCNTs) modified by D-glucose-based ionic liquids. Favorable reaction conditions (acrylic acid: n-butanol molar ratio 1:2, cyclohexane as a solvent, biocatalyst 0.150 g per 1 mmol of acrylic acid, temperature 25 °C) allowed the achievement of a 99% yield of n-butyl acrylate in 24 h. Screening of various ionic liquids showed that the most promising result was obtained if N-(6-deoxy-1-O-methoxy-α-D-glucopyranosyl)-N,N,N-trimethylammonium bis-(trifluoromethylsulfonyl)imide ([N(CH3)3GlcOCH3][N(Tf)2]) was selected in order to modify the outer surface of MWCNTs. The final SILP biocatalyst-CNTs-[N(CH3)3GlcOCH3][N(Tf)2]-CALB contained 1.8 wt.% of IL and 4.2 wt.% of CALB. Application of the SILP biocatalyst led to the enhanced activity of CALB in comparison with the biocatalyst prepared via physical adsorption of CALB onto MWCNTs (CNTs-CALB), as well as with commercially available Novozyme 435. Thus, the crucial role of IL in the stabilization of biocatalysts was clearly demonstrated. In addition, a significant stability of the developed biocatalytic system was confirmed (three runs with a yield of ester over 90%).
RESUMEN
Two types of graphite/diamond (GD) particles with different ash content was applied to prepare new electroconductive polylactide (PLA)-based nanocomposites. Four samples of nanocomposites for each type of GD particles with mass fraction 0.01, 0.05, 0.10, and 0.15 were prepared via an easily scalable method-melt blending. The samples were subjected to the studies of electrical properties via broadband dielectric spectroscopy. The results indicated up to eight orders of magnitude improvement in the electrical conductivity and electrical permittivity of the most loaded nanocomposites, in reference to the neat PLA. Additionally, the influence of ash content on the electrical conductivity of the nanocomposites revealed that technologically less-demanding fillers, i.e., of higher ash content, were the most beneficial in the light of nanofiller dispersibility and the final properties.