Herein, we report a complete additively manufactured (AM) electrochemical sensing platform. In this approach, a fully AM/3D-printed electrochemical system, using a conventional low-cost 3D printer ...(fused deposition modeling) fabricating both the conductive electrodes and the nonconductive/chemically inert electrochemical cell is reported. The electrodes (working, counter, and pseudo-reference) are AM using a conductive fused-filament comprised of a mixture of carbon black nanoparticles and polylactic acid (CB/PLA). AM components partially coated with silver ink presented a similar behavior to a conventional Ag/AgCl reference electrode. The performance of the AM working electrode was evaluated after a simple and fast polishing procedure on sandpaper and electrochemical activation in a NaOH solution (0.5 mol L–1). Following the electrochemical activation step, a considerable improvement in the electrochemical behavior (current intensity and voltammetric profile) was obtained for model analytes, such as dopamine, hexaammineruthenium(III) chloride, ferricyanide/ferrocyanide, uric acid, and ascorbic acid. Excellent repeatability (RSD = 0.4%, N = 10) and limit of detection (0.1 μmol L–1) were obtained with the all complete AM electrochemical system for dopamine analysis. The electrochemical performance of the developed system (after simple electrochemical activation of the working electrode) was similar or better than those obtained using commercial glassy carbon and screen-printed carbon electrodes. The results shown here represents a significant advance in AM (3D printing) technology for analytical chemistry.
This work presents potential applications of low-cost fused deposition modeling 3D-printers to fabricate multiuse 3D-printed electrochemical cells for flow or batch measurements as well as the ...3D-printing of electrochemical sensing platforms. Electrochemical cells and sensors were printed with acrylonitrile butadiene styrene (ABS) and conductive graphene-doped polylactic acid (G-PLA) filaments, respectively. The overall printing operation time and estimated cost per cell were 6 h and $ 6.00, respectively, while the sensors were printed within minutes (16 sensor strips of 1 × 2 cm in 10 min at a cost of $ 1.00 each sensor). The cell performance is demonstrated for the amperometric detection of tert-butylhydroquinone, dipyrone, dopamine and diclofenac by flow-injection analysis (FIA) and batch-injection analysis (BIA) using different working electrodes, including the proposed 3D-printed sensor, which presented comparable electroanalytical performance with other carbon-based electrodes (LOD of 0.1 μmol L−1 for dopamine). Raman spectroscopy and scanning electron microscopy of the 3D-printed sensor indicated the presence of graphene nanoribbons within the polymeric matrix. Electrochemical impedance spectroscopy and heterogeneous electron transfer constants (k0) for the redox probe Ru(NH3)6+3 revealed that a glassy-carbon electrode presented faster electron transfer rates than the 3D-printed sensor; however, the latter presented lower LOD values for dopamine and catechol probably due to oxygenated functional groups at the G-PLA surface.
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•Low-cost fused deposition modeling (FDM) 3D-printers to produce cells and electrodes.•Multiuse cells for flow- (FIA) and batch-injection analysis (BIA) as well for batch condition.•Designs and printing conditions accessible for any FDM 3D-printers.•Graphene-doped PLA printed sensors for voltammetric and amperometric detection.•Electroanalytical performance similar to GCE modified with carbon nanomaterials.
•Fused deposition modeling 3D-printed electrode for (bio)sensors applied to real samples.•Enzymatic glucose biosensing on 3D-printed graphene-PLA electrode in plasma.•Oxygenated groups from PLA ...matrix favored enzyme immobilization by crosslinking.•Graphene-PLA 3D-printed electrochemical response improves after surface treatment.•Rapid and precise analysis of urine and saliva by pulsed amperometry using flow system.
Additive manufacturing, also known as 3D-printing, is receiving great interest by chemists due to the easy design of novel materials, fast prototyping and reducing waste, which enables large-scale fabrication of electrochemical devices. Herein we demonstrate the development of (bio)sensors for the analysis of biological fluids using 3D-printing. Fused deposition modelling was used to fabricate (bio)sensing platforms from commercially-available filaments made of polylactic acid containing graphene (G-PLA). An enzymatic glucose biosensor fabricated on the G-PLA surface was developed and applied for glucose sensing in blood plasma using chronoamperometry. Oxygenated groups from the polymeric matrix provides suitable condition to enzyme immobilization by crosslinking with glutaraldehyde. The biosensor presented a limit of detection (LOD) of 15 μmol L−1, inter-day and intra-day precision lower than 5 %, and adequate recovery values (90–105 %) for the analysis of plasma. We also show that the surface treatment of the 3D-printed sensor (mechanical polishing followed solvent immersion) provides improved electrochemical properties for the direct detection of nitrite and uric acid. Differential-pulse voltammetry and multiple-pulse amperometry under flow conditions were evaluated and compared for the determination of both species in saliva and urine. Highlights are presented for the amperometric detection within a linear range from 0.5–250 μmol L−1 for both analytes, LODs of 0.02 and 0.03 μmol L−1 for uric acid and nitrite, respectively, and high precision (RSD < 2.1 %). This report shows the first application of 3D-printed sensors and biosensors for the analysis of real biological samples with analytical features comparable to conventional modified electrodes.
Additive manufacturing or three-dimensional (3D)-printing is an emerging technology that has been applied in the development of novel materials and devices for a wide range of applications, including ...Electrochemistry and Analytical Chemistry areas. This review article focuses on the contributions of 3D-printing technology to the development of electrochemical sensors and complete electrochemical sensing devices. Due to the recent contributions of 3D-printing within this scenario, the aim of this review is to present a guide for new users of 3D-printing technology considering the required features for improved electrochemical sensing using 3D-printed sensors. At the same time, this is a comprehensive review that includes most 3D-printed electrochemical sensors and devices already reported using selective laser melting (SLM) and fused deposition modeling (FDM) 3D-printers. The latter is the most affordable 3D-printing technique and for this reason has been more often applied for the fabrication of electrochemical sensors, also due to commercially-available conductive and non-conductive filaments. Special attention is given to critically discuss the need for the surface treatment of FDM 3D-printed platforms to improve their electrochemical performance. The insertion of biochemical and chemical catalysts on the 3D-printed surfaces are highlighted as well as novel strategies to fabricate filaments containing chemical modifiers within the polymeric matrix. Some examples of complete electrochemical sensing systems obtained by 3D-printing have successfully demonstrated the enormous potential to develop portable devices for on-site applications. The freedom of design enabled by 3D-printing opens many possibilities of forthcoming investigations in the area of analytical electrochemistry.
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•We review the contributions of 3D-printing to fabricate electrochemical sensors.•Different 3D-printing methods are compared highlighting fused deposition modeling (FDM).•Surface treatment and modification with (bio)chemical mediators for improved performance.•Strategies for fabrication of conductive filaments are presented for future applications.•3D-printing of all-in-one electrochemical devices in different designs are assessed.
•ERGO- and CRGO-modified surfaces were compared to develop sensors.•EIS showed improved electron transfer on both modified surfaces.•Higher electrochemical area and rugosity if CRGO may explain the ...higher currents.•More sensitive detection using DPV and amperometric techniques on CRGO surface.•Nanomolar DPV or amperometric detection of hydroquinone, dopamine and catechol.
The electrochemistry of hydroquinone (HQ), catechol (CT), and dopamine (DP) on a glassy-carbon electrode (GCE) modified with chemically (CRGO) and electrochemically reduced graphene oxide (ERGO) was investigated and compared for the development of amperometric and voltammetric sensors. Cyclic voltammetric measurements showed higher current on the CRGO-modified GCE, which can be explained by the higher number of sheets compared with ERGO-modified as revealed by SEM images as well as higher roughness surface monitored by AFM, indicating a higher electroactive area. Electrochemical impedance spectroscopy (EIS) revealed that both modified surfaces presented a very similar behavior (Nyquist plots) and lower resistance to electron transfer in comparison with the unmodified GCE. Considering both modified electrodes for sensing purposes, differential-pulse voltammetry (DPV) in unstirred solutions and amperometry under hydrodynamic solutions showed higher sensitivity and lower limit of detection (LOD) values for HQ, CT and DP on the CRGO-modified GCE. These results indicate that the effect of surface rugosity and electroactive area of RGO modified electrodes contribute to the improvement of sensing characteristics of phenolic compounds using either DPV or amperometric detection under flow conditions. DPV and amperometry provided LOD values between 1 and 5nmolL−1 and 12 and 55nmolL−1, respectively, while the latter offers much faster responses resulting in theoretical analytical frequency higher than 1000h−1.
Increased periods of prolonged droughts followed by severe precipitation events are expected throughout South America due to climate change. Freshwater sediments are especially sensitive to these ...changing climate conditions. The increased oscillation of water levels in aquatic ecosystems causes enhanced cycles of sediment drying and rewetting. Here we experimentally evaluate the effects of induced drought followed by a rewetting event on the release of carbon dioxide (CO2), methane (CH4), nutrients (nitrogen and phosphorus), and trace elements (iron, manganese, and zinc) from the sediment of a tropical reservoir in southeastern Brazil. Furthermore, we used bulb onions (Allium cepa) to assess the potential cytogenotoxicity of the water overlying sediments after rewetting. We found peaks in CO2 and CH4 emissions when sediments first transitioned from wet to dry, with fluxes declining as sediments dried out. CO2 emissions peaked again upon rewetting, whereas CH4 emissions remained unaltered. Our experiment also revealed average increases by up to a factor of ~5000 in the release rates of nutrients and trace elements in water overlying sediments after rewetting. These increased release rates of potentially toxic compounds likely explain the lower replication of Allium cepa cells (up to 22% reduction) exposed to water overlying sediments after rewetting. Our findings suggest that increased events of drought followed by rewetting may lead to a range of changes in freshwater ecosystems, including nutrient enrichment, increased toxicity following resuspension of contaminants, and higher emission of greenhouse gases to the atmosphere.
Celotno besedilo
Dostopno za:
DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
The innate immune system, a cornerstone for organismal resilience against environmental and microbial insults, is highly conserved across the evolutionary spectrum, underpinning its pivotal role in ...maintaining homeostasis and ensuring survival. This review explores the evolutionary parallels between mammalian and insect innate immune systems, illuminating how investigations into these disparate immune landscapes have been reciprocally enlightening. We further delve into how advancements in mammalian immunology have enriched our understanding of insect immune responses, highlighting the intertwined evolutionary narratives and the shared molecular lexicon of immunity across these organisms. Therefore, this review posits a holistic understanding of innate immune mechanisms, including immunometabolism, autophagy and cell death. The examination of how emerging insights into mammalian and vertebrate immunity inform our understanding of insect immune responses and their implications for vector-borne disease transmission showcases the imperative for a nuanced comprehension of innate immunity’s evolutionary tale. This understanding is quintessential for harnessing innate immune mechanisms' potential in devising innovative disease mitigation strategies and promoting organismal health across the animal kingdom.
On November 2015, one of Brazil's most important watersheds was impacted by the mine waste from Fundão dam collapse in Mariana. The mine waste traveled over 600 km along the Doce River before ...reaching the sea, causing severe devastation along its way. Here we assessed trace element concentrations and cytogenotoxic effects of the released mine waste. Water samples were collected along the Doce River ten days after the disaster in two impacted sites and one non-impacted site. Sampling points were located hundreds of kilometers downstream of the collapsed dam. Water samples were used for trace element quantification and to run an experiment using Allium cepa to test cytogenotoxicity. We found extremely high concentrations of particulate Fe, Al, and Mn in the impacted sites. We observed cytogenotoxic effects such as alterations in mitotic and phase indexes, and enhanced frequency of chromosomal aberrations. Our results indicate interferences in the cell cycle in impacted sites located hundreds of kilometers downstream of the disaster. The environmental impacts of the dam collapse may not only be far-reaching but also very likely long-lasting, because the mine waste may persist in the Doce River sediment for decades.
•Higher concentrations of particulate metals were found in impacted sites.•Cytogenotoxic effects were found in the impacted sites.•Mining waste affected genetic aspects of Allium cepa.•Impacts of the tragedy are far-reaching and long-lasting.
•Legumes provide ecosystem services increasing maize yield in Amazonian agrosystem.•Base cations, organic matter, nitrogen uptake are increased by leguminous biomass.•Ecosystem services style ...approachcan ensure feasibilityin Amazonianagrosystems.
In the Amazonian periphery, there are sources of numerous disservices, including deforestation, loss of wildlife habitat and biodiversity erosion. However, there are great opportunities to adopt appropriate agricultural management practices to take advantage of the benefits of ecosystem services for sustainable agricultural intensification. Thus, the aim of this work was to evaluate the effects of certain ecosystem services provided by combined use of legumes with residue of low- and high-quality on soil quality indicators, nitrogen use efficiency and sustainability of maize grain yield in infertile tropical soil. The overarching objective is to determine how ecosystem services can contribute to the improvement of land-use policy to ensure the sustainability of cultivated lands, in such a way that forest can be preserved by avoiding deforestation of other new areas through shifting cultivation systems. Four leguminous tree species were used, two with high-quality residues Leucaena leucocephala (leucaena) and Gliricidia sepium (gliricidia) and two with low-quality residues Clitoria fairchildiana (clitoria) and Acacia mangium (acacia). Maize grain yield was evaluated between 2011 and 2017 in these treatments. In 2018, to assess how ecosystem services affect crop performance, the treatmentswere divided into ten treatments with and without urea.We conclude that increased uptake of inorganic and organic N by maize resulting from improvement of the soil quality indicators may allow agricultural intensification. This improvement can help meet the challenges of sustainability and feasibility of agroecosystems of the Amazonian periphery by making the agroecosystem more productive year by year. Therefore, our results confirm that the utilization of an ecosystem services style approach can help meet the challenges of sustainability and feasibility in agrosystems of the Amazonian periphery. In addition, these results can contribute to the development of land-use policy in the Amazonian periphery, aiming for the intensification of agriculture in cropped areas to avoid deforestation of new areas from shifting cultivation systems.
•The electrochemistry of phenolic compounds is affected by dimensions of MWCNT.•Small diameter MWCNT presented higher electrocatalytic activity (50–150mV shift).•Substantial increase (3-fold) in ...current was verified at the small diameter MWCNT.•Increased defect density was in agreement with nanotube diameter.•Amperometric measurements were also improved (up to 4-fold gain in sensitivity).
The electrochemical activity of functionalized multi-walled carbon nanotubes (MWCNTs) of different sizes (D×L: 100–170nm×5–9μm and 6–9nm×5μm, corresponding to LD- and SD-MWCNTs, respectively) towards the electro-oxidation of hydroquinone (HQ), tert-butylhydroquinone (TBHQ), catechol (CT), and dopamine (DP) was investigated. The electrochemical response for all phenolic compounds at MWCNT-modified glassy-carbon electrodes (GCEs) presented a short decrease in the overpotential of the oxidation reactions (<100mV); however, the values of ΔEp (peak-to-peak separation) were considerably reduced at the LD-MWCNT surface and even more at the SD-MWCNT-modified GCE in comparison with the unmodified GCE. This result indicates the higher electrocatalytic activity of SD-MWCNTs, which is in agreement with the nanotube diameter and the increased defect density, as revealed by XRD and Raman spectroscopic measurements, respectively. Additionally, a substantial increase (three-fold) in the current for the oxidation of HQ, TBHQ, and DP at the SD-MWCNT-modified GCE was obtained. Amperometric measurements also revealed the improved performance of SD-MWCNT-modified GCE (up to four-fold increase in sensitivity).
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