Tuning the Chemical and Electrochemical Properties of Paper-Based Carbon Electrodes by Pyrolysis of Polydopamine.

Electrochemical paper-based analytical devices represent an important platform for portable, low-cost, affordable, and decentralized diagnostics. For this kind of application, chemical functionalization plays a pivotal role to ensure high clinical performance by tuning surface properties and the area of electrodes. However, controlling different surface properties of electrodes by using a single functionalization route is still challenging. In this work, we attempted to tune the wettability, chemical composition, and electroactive area of carbon-paper-based devices by thermally treating polydopamine (PDA) at different temperatures. PDA films were deposited onto pyrolyzed paper (PP) electrodes and thermally treated in the range of 300-1000 °C. After deposition of PDA, the surface is rich in nitrogen and oxygen, it is superhydrophilic, and it has a high electroactive area. As the temperature increases, the surface becomes hydrophobic, and the electroactive area decreases. The surface modifications were followed by Raman, X-ray photoelectron microscopy (XPS), laser scanning confocal microscopy (LSCM), contact angle, scanning electron microscopy (SEM-EDS), electrical measurements, transmission electron microscopy (TEM), and electrochemical experiments. In addition, the chemical composition of nitrogen species can be tuned on the surface. As a proof of concept, we employed PDA-treated surfaces to anchor [AuCl4]- ions. After electrochemical reduction, we observed that it is possible to control the size of the nanoparticles on the surface. Our route opens a new avenue to add versatility to electrochemical interfaces in the field of paper-based electrochemical biosensors.

Scalable and green formation of graphitic nanolayers produces highly conductive pyrolyzed paper toward sensitive electrochemical sensors.

While pyrolyzed paper (PP) is a green and abundant material that can provide functionalized electrodes with wide detection windows for a plethora of targets, it poses long-standing challenges against sensing assays such as poor electrical conductivity, with resistivities generally higher than 200.0 mΩ cm (e.g., gold and silver show resistivities 1000-fold lower, ∼0.2 mΩ cm). In this regard, the fundamental hypothesis that drives this work is whether a scalable, cost-effective, and eco-friendly strategy is capable of significantly reducing the resistivity of PP electrodes toward the development of sensitive electrochemical sensors, whether faradaic or capacitive. We address this hypothesis by simply annealing PP under an isopropanol atmosphere for 1 h, reaching resistivities as low as 7 mΩ cm. Specifically, the annealing of PP at 800 or 1000 °C under isopropanol vapor leads to the formation of a highly graphitic nanolayer (∼15 nm) on the PP surface, boosting conductivity as the delocalization of π electrons stemming from carbon sp2 is favored. The reduction of carbonyl groups and the deposition of dehydrated isopropanol during the annealing process are hypothesized herein as the dominant PP graphitization mechanisms. Electrochemical analyses demonstrated the capability of the annealed PP to increase the charge-transfer kinetics, with the optimum heterogeneous standard rate constant being roughly 3.6 × 10-3 cm s-1. This value is larger than the constants reported for other carbon electrodes and indium tin oxide. Furthermore, freestanding fingers of the annealed PP were prototyped using a knife plotter to fabricate impedimetric on-leaf electrodes. These wearable sensors ensured the real-time and in situ monitoring of the loss of water content from soy leaves, outperforming non-annealed electrodes in terms of reproducibility and sensitivity. Such an application is of pivotal importance for precision agriculture and development of agricultural inputs. This work addresses the foundations for the achievement of conductive PP in a scalable, low-cost, simple, and eco-friendly way, i.e. without producing any liquid chemical waste, providing new opportunities to translate PP-based sensitive electrochemical devices into practical use.

How lignin sticks to cellulose-insights from atomic force microscopy enhanced by machine-learning analysis and molecular dynamics simulations.

Elucidating cellulose-lignin interactions at the molecular and nanometric scales is an important research topic with impacts on several pathways of biomass valorization. Here, the interaction forces between a cellulosic substrate and lignin are investigated. Atomic force microscopy with lignin-coated tips is employed to probe the site-specific adhesion to a cellulose film in liquid water. Over seven thousand force-curves are analyzed by a machine-learning approach to cluster the experimental data into types of cellulose-tip interactions. The molecular mechanisms for distinct types of cellulose-lignin interactions are revealed by molecular dynamics simulations of lignin globules interacting with different cellulose Iß crystal facets. This unique combination of experimental force-curves, data-driven analysis, and molecular simulations opens a new approach of investigation and updates the understanding of cellulose-lignin interactions at the nanoscale.

Toxicity mitigation and biodistribution of albumin corona coated graphene oxide and carbon nanotubes in Caenorhabditis elegans.

In this work, the toxicity and biodistribution of graphene oxide (GO) and oxidized multi-walled carbon nanotubes (MWCNT) were investigated in Caenorhabditis elegans. Bovine serum albumin (BSA) was selected as a model protein to evaluate the influence of protein corona formation on materials physicochemical properties, colloidal stability, and toxicity. Biological assays were performed to assess the effects of bare and albumin corona coated materials on survival, oxidative stress, intestinal barrier permeability, growth, reproduction, and fertility. Critical alterations in topography, surface roughness and chemistry of GO and MWCNT were observed due to albumin corona formation. These modifications were associated with changes in colloidal stability of materials and prevention of their aggregation and sedimentation in nematode testing medium. Both GO and MWCNT caused damage to nematode survival, growth, reproduction, and fertility, as well as enhanced oxidative stress and permeability of the intestinal barrier. But GO was more toxic than MWCNT to C. elegans, especially at long-term assays. Albumin corona mitigated 100% of acute and chronic effects of MWCNT. In contrast, the negative effects of GO were not completely mitigated; GO inhibited 16.2% of nematode growth, 86.5% of reproduction, and 32.0% of fertility at the highest concentration evaluated (10 mg L-1), while corona coated GO mitigated 50% and 100% of fertility and growth, respectively. Confocal Raman spectroscopy imaging was crucial to point out that bare and albumin corona coated GO and MWCNT crossed the C. elegans intestinal barrier reaching its reproductive organs. However, BSA corona protected the nematodes targeted organs from negative effects from MWCNT and blocked its translocation to other tissues, while coated GO was translocated inside the nematode affecting the functionality of crucial organs. In addition, coated MWCNT was excreted after 2 h of food resumption, whereas coated GO still accumulated in the nematode intestine. Our results demonstrate that the materials different translocation and excretion patterns in C. elegans had a relation to the impaired physiological functions of primary and secondary organs. This work is a contribution towards a better understanding of the impacts of protein corona on the toxicity of graphene oxide and carbon nanotubes; essential information for biological applications and nanosafety.

Fast and efficient electrochemical thinning of ultra-large supported and free-standing MoS2 layers on gold surfaces.

Molybdenum disulfide (MoS2) is a very promising layered material for electrical, optical, and electrochemical applications because of its unique and outstanding properties. To unlock its full potential, among different preparation routes, electrochemistry has gain interest due to its simple, fast, scalable and simple instrumentation. However, obtaining large-area monolayer MoS2 that will enable the fabrication of novel electronic and electrochemical devices is still challenging. In this work, we reported a simple and fast electrochemical thinning process that results in ultra-large MoS2 down to monolayer on Au surfaces. The high affinity of MoS2 by Au surfaces enables the removal of bulk layers while preserving the first layer attached to the electrode. With a proper choice of the applied potential, more than 90% of the bulk regions can be removed from large-area MoS2 crystals, as confirmed by atomic force microscopy, photoluminescence, and Raman spectroscopy. We further address a set of contributions that are helpful to elucidate the features of MoS2, namely, the hyphenation of electrochemistry and optical microscopy for real-time observation of the thinning process that was revealed to occur from the edges to the center of the flake, an image treatment to estimate the thinning area and thinning rate, and the preparation of free-standing MoS2 layers by electrochemically thinning bulk flakes on microhole-structured Ni/Au meshes.

Mitigation of graphene oxide toxicity in C. elegans after chemical degradation with sodium hypochlorite.

Graphene oxide (GO) is a promising and strategic carbon-based nanomaterial for innovative and disruptive technologies. It is therefore essential to address its environmental health and safety aspects. In this work, we evaluated the chemical degradation of graphene oxide by sodium hypochlorite (NaClO, bleach water) and its consequences over toxicity, on the nematode Caenorhabditis elegans. The morphological, chemical, and structural properties of GO and its degraded product, termed NaClO-GO, were characterized, exploring an integrated approach. After the chemical degradation of GO at room temperature, its flake size was reduced from 156 to 29 nm, while NaClO-GO showed changes in UV-vis absorption, and an increase in the amount of oxygenated surface groups, which dramatically improved its colloidal stability in moderately hard reconstituted water (EPA medium). Acute and chronic exposure endpoints (survival, growth, fertility, and reproduction) were monitored to evaluate material toxicities. NaClO-GO presented lower toxicity at all endpoints. For example, an increase of over 100% in nematode survival was verified for the degraded material when compared to GO at 10 mg L-1. Additionally, enhanced dark-field hyperspectral microscopy confirmed the oral uptake of both materials by C. elegans. Finally, this work represents a new contribution toward a better understanding of the links between the transformation of graphene-based materials and nanotoxicity effects (mitigation), which is mandatory for the safety improvements that are required to maximize nanotechnological benefits to society.

Deterministic control of surface mounted metal-organic framework growth orientation on metallic and insulating surfaces.

Surface-Mounted Metal-Organic Frameworks (SURMOFs) are promising materials with a wide range of applications and increasing interest in different technological fields. The use of SURMOFs as both the active and passive tail in electronic devices is one of the most exciting possibilities for such a hybrid material. In such a context, the adhesion, roughness, and crystallinity control of SURMOF thin films are challenging and have limited their application in new functional electronic devices. Self-assembled monolayers (SAMs), which ensure the effective attachment of the SURMOF onto substrates, also play a critical role that can profoundly affect the SURMOF growth mechanism. Herein, we demonstrate that the deterministic control of the SAM chain length influences the preferential orientation of SURMOF films. As the SAM chain length increases, HKUST-1 thin films tend to change their preferential orientation from the [111] towards the [100] direction. Such control can be achieved on both electrically conducting and insulating substrates, opening the possibility of having the very same preferential crystalline orientation on surfaces of different nature, which is of fundamental importance for SURMOF-based functional electronic devices.

Exploring the Hierarchical Structure and Alignment of Wood Cellulose Fibers for Bioinspired Anisotropic Polymeric Composites.

Materials found in nature have their properties tuned by the chemical composition and hierarchical organization of their structures. Wood is one example of natural material which has properties tuned by its multi-scale hierarchical organization. The cellulose microfibril angle is critical for physical and mechanical properties of wood. On the other hand, polymeric composites containing fibrillar additives, like cellulose fibers, are widespread and have exceptional mechanical properties, which enable them to be used as structural materials. However, obtaining polymer composites with well-aligned cellulose fibers is a challenging task. This work aims to explore the hierarchical structure and alignment of cellulose fibers from wood in polymeric composites with anisotropic mechanical properties, inspired by what trees naturally do. In this sense, cellulosic material from wood was analyzed on a multi-scale; impregnation with polyethylene and densification were performed to form composites; and their mechanical properties were correlated with fiber angles in composite specimens. Moreover, polymer addition to the cellulosic backbone has tremendously increased the material resistance to wetting and chemical oxidation.

Analysis of the effects of mesoporous silica particles SBA-15 and SBA-16 in Streptococcus pneumoniae transformation process.

Streptococcus pneumoniae are natural competent bacteria which requires the presence of a pheromone-like molecule to do the transformation process. This study verified the influence of mesoporous silica (SBA-15 and SBA-16) on the transformation process in S. pneumoniae using a donor DNA obtained from a mutant strain of this microorganism (Sp360∆luxS). The results showed that mesoporous silica SBA-15 and SBA-16 particles doubled the transformation ratio frequency compared with negative control (without nanoparticles) in using SBA-15 (ratio 1.81 ± 0.04) and SBA-16 (ratio 2.18 ± 0.22). We demonstrated the how mesoporous silica nanoparticles were able to increase the pneumococcus transformations, which could possibly lead to the acquisition of virulence factor genes and resistance of antibiotics.

The Positive Fate of Biochar Addition to Soil in the Degradation of PHBV-Silver Nanoparticle Composites.

The environmental contamination of soils by polymeric and nanomaterials is an increasing global concern. Polymeric composites containing silver nanoparticles (AgNP) are collectively one of the most important products of nanotechnology due to their remarkable antimicrobial activity. Biochars are a promising resource for environmental technologies for remediation of soils considering their high inorganic and organic pollutant adsorption capacity and microbial soil consortium stimulation. In this work we report, for the first time, the use of biochar material as a tool to accelerate the degradation of polyhydroxybutyrate- co-valerate (PHBV) and PHBV composites containing AgNP in a tropical soil system, under laboratory conditions. This positive effect is associated with microbial community improvement, which increased the degradation rate of the polymeric materials, as confirmed by integrated techniques for advanced materials characterization. The addition of 5-10% of sugarcane bagasse biochar into soil has increased the degradation of these polymeric materials 2 to 3 times after 30 days of soil incubation. However, the presence of silver nanoparticles in the PHBV significantly reduced the degradability potential of this nanocomposite by the soil microbial community. These results provide evidence that AgNP or Ag+ ions caused a decline in the total number of bacteria and fungi, which diminished the polymer degradation rate in soil. Finally, this work highlights the great potential of biochar resources for application in soil remediation technologies, such as polymeric (nano)material biodegradation.

Microstructural characterization of nanocellulose foams prepared in the presence of cationic surfactants.

In this work, we explore the architecture of highly porous foams based on cellulose nanofibers (CNFs) prepared by using cationic surfactants (e.g., C12TAB, C14TAB, and C16TAB) as modifying agents. The addition of surfactants to CNF suspensions led the nanoparticles surface to be covered by these molecules, reducing the ζ-potential from -35 to -8 mV, which, together with hydrophobic interactions of adsorbed surfactants, causes CNF flocculation. After freeze-casting and lyophilization, mechanical properties and pores structure of the low-density foams obtained (15.6-30.9 mg cm-3) proved to be strongly dependent on nanofibers agglomeration degree. The primary causes of such dependence could not be observable by scanning electron microscopy but were found to be very significant on X-ray microtomography analysis. Total porosity, pore-size, and wall thickness of the foams were calculated and related to the surfactant chain size. Surface areas from 4.7 to 48.6 m2 g-1, obtained by n-decane adsorption, are reported.

Coating carbon nanotubes with humic acid using an eco-friendly mechanochemical method: Application for Cu(II) ions removal from water and aquatic ecotoxicity.

In this work, industrial grade multi-walled carbon nanotubes (MWCNT) were coated with humic acid (HA) for the first time by means of a milling process, which can be considered an eco-friendly mechanochemical method to prepare materials and composites. The HA-MWCNT hybrid material was characterized by atomic force microscopy (AFM), scanning electron microscopies (SEM and STEM), X-ray photoelectron spectroscopy (XPS), termogravimetric analysis (TGA), and Raman spectroscopy. STEM and AFM images demonstrated that the MWCNTs were efficiently coated by the humic acid, thus leading to an increase of 20% in the oxygen content at the nanotube surface as observed by the XPS data. After the milling process, the carbon nanotubes were shortened as unveiled by SEM images and the values of ID/IG intensity ratio increased due to shortening of the nanotubes and increasing in the number defects at the graphitic structure of carbon nanotubes walls. The analysis of TGA data showed that the quantity of the organic matter of HA on the nanotube surface was 25%. The HA coating was responsible to favor the dispersion of MWCNTs in ultrapure water (i.e. -42mV, zeta-potential value) and to improve their capacity for copper removal. HA-MWCNTs hybrid material adsorbed 2.5 times more Cu(II) ions than oxidized MWCNTs with HNO3, thus evidencing that it is a very efficient adsorbent material for removing copper ions from reconstituted water. The HA-MWCNTs hybrid material did not show acute ecotoxicity to the tested aquatic model organisms (Hydra attenuata, Daphnia magna, and Danio rerio embryos) up to the highest concentration evaluated (10mgL-1). The results allowed concluding that the mechanochemical method is effective to coat carbon nanotubes with humic acid, thus generating a functional hybrid material with low aquatic toxicity and great potential to be applied in environmental nanotechnologies such as the removal of heavy metal ions from water.

Flexible and Foldable Fully-Printed Carbon Black Conductive Nanostructures on Paper for High-Performance Electronic, Electrochemical, and Wearable Devices.

In this work, we demonstrate the first example of fully printed carbon nanomaterials on paper with unique features, aiming the fabrication of functional electronic and electrochemical devices. Bare and modified inks were prepared by combining carbon black and cellulose acetate to achieve high-performance conductive tracks with low sheet resistance. The carbon black tracks withstand extremely high folding cycles (>20 000 cycles), a new record-high with a response loss of less than 10%. The conductive tracks can also be used as 3D paper-based electrochemical cells with high heterogeneous rate constants, a feature that opens a myriad of electrochemical applications. As a relevant demonstrator, the conductive ink modified with Prussian-blue was electrochemically characterized proving to be very promising toward the detection of hydrogen peroxide at very low potentials. Moreover, carbon black circuits can be fully crumpled with negligible change in their electrical response. Fully printed motion and wearable sensors are additional examples where bioinspired microcracks are created on the conductive track. The wearable devices are capable of efficiently monitoring extremely low bending angles including human motions, fingers, and forearm. Here, to the best of our knowledge, the mechanical, electronic, and electrochemical performance of the proposed devices surpasses the most recent advances in paper-based devices.

Structural aspects of graphitic carbon modified SBA-15 mesoporous silica and biological interactions with red blood cells and plasma proteins.

Functional mesoporous materials have been worldwide studied for different applications. Mesoporous silicas are highlighted due to the synthetic possibilities for the preparation of such materials with different particle sizes and morphologies, and controlled pores sizes and structures. Moreover, the silica superficial silanol groups are explored in several chemical modifications, leading to functional materials with tuned functionalities and properties. In this work, an organo-functionalization and pyrolysis synthetic procedure is used to obtain graphitic carbon modified mesoporous SBA-15 silica. The carbon content was tuned during the functionalization step, and the graphitic nanodomains were formed in the pores surface and particles outer surface. Textural and small angle X-ray diffraction analysis accessed the presence of the carbon nanostructures inside the SBA-15 mesopores. Advanced microanalysis using electron energy loss spectroscopy coupled to a transmission electron microscope had confirmed the carbon distribution along the silica pores, which gives higher hydrophobicity and changed the interaction of the mesoporous material with biological systems. Finally, the influence of the surface modification with graphitic carbon species over the interaction with human red blood cells (hemolysis) and human blood plasma (protein corona formation) was elucidated for the very first time for this kind of functional materials. It was observed that the graphitic carbon species considerably reduced the hemolytic effect of the silica particles, and was responsible for modulating the loading and composition of the hard corona plasma proteins. This work deepness the fundamental knowledge on the interaction between such nanomaterials and biological systems, one step further the use of these modified silicas in biomedical applications.

Direct Drawing Method of Graphite onto Paper for High-Performance Flexible Electrochemical Sensors.

A simple and fast fabrication method to create high-performance pencil-drawn electrochemical sensors is reported for the first time. The sluggish electron transfer observed on bare pencil-drawn surfaces was enhanced using two electrochemical steps: first oxidizing the surface and then reducing it in a subsequent step. The heterogeneous rate constant was found to be 5.1 × 10-3 cm s-1, which is the highest value reported so far for pencil-drawn surfaces. We mapped the origin of such performance by atomic force microscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy. Our results suggest that the oxidation process leads to chemical and structural transformations on the electrode surface. As a proof-of-concept, we modified the pencil-drawn surface with Meldola's blue to electrocatalytically detect nicotinamide adenine dinucleotide (NADH). The electrochemical device exhibited the highest catalytic constant (1.7 × 105 L mol-1 s-1) and the lowest detection potential for NADH reported so far in paper-based electrodes.

Functionalization of Mesoporous Silicas as Strategy for Obtaining Nanocomposites with Controlled Graphitic Domains Quantity and Carbon Content.

We report in this work the use of a synthetic procedure to prepare silica-carbon composites with controlled carbon content and number of graphitic nanocarbon domains. This synthetic protocol was applied to prepare carbon nanostructures supported at two different amorphous silicas that have similar disordered pore system structure but different specific surface areas and pore volumes. The carbon nanostructures were obtained by the silica surface grafting with different amounts of 2,3-dihydroxynaphthalene (DN) using a dehydration reaction followed by pyrolysis at temperatures between 973 and 1173 K. We observed that the number of the graphitic nanodomains and the carbon loading at the pyrolysed samples could be tuned by the synthetic parameters during the functionalization and thermal treatment steps, as by the textural properties of the support.

Activated carbon from pyrolysed sugarcane bagasse: Silver nanoparticle modification and ecotoxicity assessment.

Activated carbon from pyrolysed sugarcane bagasse (ACPB) presented pore size ranges from 1.0 to 3.5nm, and surface area between 1200 and 1400m(2)g(-1) that is higher than commonly observed to commercial activated carbon. The ACPB material was successfully loaded with of silver nanoparticles with diameter around 35nm (0.81wt.%). X-ray photoelectron spectroscopy (XPS) analyses showed that the material surface contains metallic/Ag(0) (93.60wt.%) and ionic/Ag(+) states (6.40wt.%). The adsorption capacity of organic model molecules (i.e. methylene blue and phenol) was very efficient to ACPB and ACPB loaded with silver nanoparticles (ACPB-AgNP), indicating that the material modification with silver nanoparticles has not altered its adsorption capacity. ACPB-AgNP inhibited bacteria growth (Escherichia coli), it is a promising advantage for the use of these materials in wastewater treatment and water purification processes. However, ACPB-AgNP showed environmental risks, with toxic effect to the aquatic organism Hydra attenuata (i.e. LC50 value of 1.94mgL(-1)), and it suppressed root development of Lycopersicum esculentum plant (tomato). Finally, this work draw attention for the environmental implications of activated carbon materials modified with silver nanoparticles.

Ion-exchange properties of imidazolium-grafted SBA-15 toward AuCl4(-) anions and their conversion into supported gold nanoparticles.

Imidazolium groups were successfully prepared and grafted on the surface of SBA-15 mesoporous silica. The ion-exchange properties of the functionalized porous solid (SBA-15/R(+)Cl(-)) toward AuCl(4)(-) anions were evaluated through an ion-exchange isotherm. The calculated values of the equilibrium constant (log ß = 4.47) and the effective ion-exchange capacity (t(Q) = 0.79 mmol g(-1)) indicate that the AuCl(4)(-) species can be loaded and strongly retained on the functionalized surface as counterions of the imidazolium groups. Subsequently, solids containing different amounts of AuCl(4)(-) ions were submitted to a chemical reduction process with NaBH(4), converting the anionic gold species into supported gold nanoparticles. The plasmon resonance bands, the X-ray diffraction patterns, and transmission electron microscopy images of the supported gold nanoparticles before and after thermal treatment at 973 K indicate that the metal nanostructures are highly dispersed and stabilized by the host environment.