The storage stability and corrosive character of soybean biodiesel stabilised with tert-butylhydroquinone (TBHQ) was investigated through static immersion corrosion tests. Coupons of carbon steel and ...galvanised steel were immersed in soybean biodiesel with and without TBHQ for 12 weeks. Measurements of total acid number, peroxide value, oxidation stability (Rancimat induction period), metal release, and TBHQ consumption at different stages of corrosion were performed. After 12 weeks of the static immersion test with both steels, the non-stabilised biodiesels presented induction times below the EN 14214 limit (6 h); these results were in agreement with increase in the peroxide values. Zinc release was only detected in the non-stabilised biodiesel exposed to galvanised steel, whilst iron was not detected in any biodiesel samples exposed to carbon steel. The absence of zinc in the TBHQ-doped biodiesel exposed to galvanised steel indicates that TBHQ may have acted as a corrosion inhibitor. Additionally, TBHQ was rapidly consumed in the first 3 days of experiments, providing evidence of its activity. For a storage period of up to 56 days, both galvanised and carbon steels were shown to be compatible with biodiesel even in the absence of an antioxidant. The presence of zinc (>2 (mu)g g(-1) after 28 days of immersion) due to corrosion did not promote biodiesel deterioration.
► Highly rapid, selective and sensitive amperometric detection of H2O2 in milk. ► Prussian-blue modified electrode with improved stability and precision. ► Association with batch-injection analysis ...provided high analytical frequency. ► Satisfactory recovery values for milk analysis.
We report a highly rapid, precise, selective and sensitive analytical method for the determination of hydrogen peroxide in milk using a batch-injection analysis (BIA) with amperometric detection at a Prussian-blue bulk modified graphite-composite electrode. An electronic micropipette injected 100μL aliquots of 10-fold diluted samples (high and low-fat milk) directly onto the modified electrode immersed in the BIA cell. The analytical features of our proposed method includes low RSD between injections (0.76%, n=9), low detection limit (10μmolL−1), elevated analytical frequency (up to 80h−1) and satisfactory recovery values for spiked samples. A fresh and highly reproductive electrode surface can be easily obtained by simple mechanical polishing (RSD=1.6%, n=5). The storage stability of the PB-modified graphite-composite surpassed 1year keeping equivalent performance as initially presented. The association of BIA with an improved amperometric detector provides great promise for routine monitoring of hydrogen peroxide in milk and other beverages.
•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.
Paracetamol is an active ingredient commonly found in pharmaceutical formulations in combination with one of the following compounds: codeine, orphenadrine, promethazine, scopolamine, and tramadol. ...In this work, we propose a unique analytical method for determination of these active ingredients in pharmaceutical samples. The method is based on capillary electrophoresis with capacitively coupled contactless conductivity detection. The separation was achieved on a fused silica capillary (50 cm total length, 40 cm effective length, and 50 μm id) using an optimized background electrolyte composed of 20 mmol/L β‐alanine/4 mmol/L sodium chloride/4 μmol/L sodium hydroxide (pH 9.6). Each sample can be analyzed in a single run (≤2 min) and the limits of detection were 2.5, 0.62, 0.63, 2.5, 15, and 1.6 μmol/L for scopolamine, tramadol, orphenadrine, promethazine, codeine, and paracetamol, respectively. Recovery values for spiked samples were between 94 and 104%.
Background
Asthma is a syndrome characterized by airway inflammation and obstruction. Due to its heterogeneity, the difficulties in asthma diagnosis and treatment make the discovery of new biomarkers ...a focus of research. So, we determined the differential miRNA expression of eosinophils between healthy and asthmatic patients and to establish a differentially expressed miRNA profile detectable in sera for use as biomarker.
Methods
MicroRNAs from peripheral eosinophils from healthy and asthmatic subjects were isolated and analyzed by next‐generation sequencing and confirmed by quantitative PCR in 29 asthmatics and 10 healthy individuals. The levels of serum miRNAs were performed by quantitative PCR in 138 asthmatics and 39 healthy subjects. Regression analysis and Random Forest models were performed.
Results
We found a set of miRNAs whose expression differs between eosinophils from asthmatics and healthy subjects. These miRNAs can classify asthmatics into two clusters that differed in the number of eosinophils and periostin concentration in serum. Some of these miRNAs were also confirmed in sera, as miR‐185‐5p which discriminates asthmatics from healthy subjects. Together with other two miRNAs, miR‐185‐5p allowed us to create a logistic regression model to discriminate better both conditions and a Random Forest model that can even sort the asthmatics into intermittent, mild persistent, moderate persistent, and severe persistent asthma.
Conclusion
Our data show that miRNAs profile in eosinophils can be used as asthma diagnosis biomarker in serum and that this profile is able to rank asthma severity.
Eosinophils from asthmatics present a different profile in microRNAs (miRNAs) compared to eosinophils from healthy subjects. As eosinophils obtention from patients is not a standardized method, we analyzed these miRNAs in serum showing that miRNAs profile expression in this biofluid can be used for asthma diagnosis and for severity classification.
We report a new fast method for the simultaneous determination of amoxicillin, clavulanate, and potassium by capillary electrophoresis with capacitively coupled contactless conductivity detection. ...Samples containing potassium as the cation, and both amoxicillin and clavulanate as anions were determined simultaneously in a single run (in less than 45 s) using 10 mmol/L of both 2‐amino‐2‐hydroxymethyl‐propane‐1,3‐diol and 3‐{2‐hydroxy‐1,1‐bis(hydroxymethyl)ethylamino}‐1‐propanesulfonic acid (pH 8.4) as the background electrolyte. Limits of detection were 25.0, 5.0, and 4.0 μmol/L for amoxicillin, clavulanate, and potassium, respectively. The proposed method is inexpensive, simple, fast (75 injections h−1), environment friendly (minimal waste generation), and accurate (recovery values between 98 and 103%). The results obtained with the proposed method were statistically similar (95% confidence level) to those obtained by using high‐performance liquid chromatography (amoxicillin and clavulanate) and flame photometry (potassium).
Low oxidation stability is the main drawback of biodiesels and biokerosenes that is overcome by using antioxidants, which can be combined due to synergistic effects. This paper demonstrates that ...3D-printed electrochemical devices can be applied to biofuel electroanalysis, including the monitoring of oxidation stability by quantifying the antioxidant content in biofuels. Fabrication requires 3D-printed acrylic templates at which a polylactic acid (PLA) filament with conducting carbon-black filling sensors is extruded by a 3D pen. The antioxidants butyl hydroxyanisole (BHA) and
tert
-butylhydroquinone (TBHQ) are the most employed additives in biodiesel production, and thus, their electrochemical behavior was investigated; 2,6-ditertbutylphenol (2,6-DTBP) was included in this investigation because it is commonly added to biokerosenes. The electrochemical surface treatment of the 3D-printed electrodes improved the current responses of all antioxidants; however, the electrochemical oxidation of TBHQ was clearly more affected by an electrocatalytic action shifting its oxidation towards less positive potentials (~200 mV), which resulted in a better separation of TBHQ and BHA oxidation peaks (+0.4 and +0.6 V vs Ag|AgCl, respectively). The oxidation of 2,6-DTBP occurred at more positive potentials (+1.2 V vs Ag|AgCl). The simultaneous determination of TBHQ and BHA by differential-pulse voltammetry resulted in linear responses in the range 0.5 and 175 μmol L
−1
with limits of detection and quantification of 0.15 μmol L
−1
and 0.5 μmol L
−1
, respectively. The presence of Fe
3+
, Cu
2+
, Pb
2+
, Mn
2+
, Cd
2+
, and Zn
2+
, even in high concentrations, did not interfere in the determination of TBHQ and BHA. The determination of 2,6-DTBP in biokerosene was achieved by cyclic voltammetry. All relative standard deviations (RSD) were lower than 6.0 %, indicating adequate precision of the methods. Spiked biofuel samples were analyzed (after dilution in electrolyte) and recovery values between 85 and 120% were obtained, which indicates absence of sample matrix effects.
Graphical abstract
The fabrication of carbon black/polylactic acid (PLA) electrodes using a 3D printing pen is presented and compared with electrodes obtained by a desktop fused deposition modelling (FDM) 3D printer. ...The 3D pen was used for the fast production of electrodes in two designs using customized 3D printed parts to act as template and guide the reproducible application of the 3D pen: (i) a single working electrode at the bottom of a 3D-printed cylindrical body and (ii) a three-electrode system on a 3D-printed planar substrate. Both devices were electrochemically characterized using the redox probe Fe(CN)63−/4- via cyclic voltammetry, which presented similar performance to an FDM 3D-printed electrode or a commercial screen-printed carbon electrode (SPE) regarding peak-to-peak separation (ΔEp) and current density. The surface treatment of the carbon black/PLA electrodes fabricated by both 3D pen and FDM 3D-printing procedures provided substantial improvement of the electrochemical activity by removing excess of PLA, which was confirmed by scanning electron microscopic images for electrodes fabricated by both procedures. Structural defects were not inserted after the electrochemical treatment as shown by Raman spectra (iD/iG), which indicates that the use of 3D pen can replace desktop 3D printers for electrode fabrication. Inter-electrode precision for the best device fabricated using the 3D pen (three-electrode system) was 4% (n = 5) considering current density and anodic peak potential for the redox probe. This device was applied for the detection of 2,4,6-trinitrotoluene (TNT) via square-wave voltammetry of a single-drop of 100 μL placed upon the thee-electrode system, resulting in three reduction peaks commonly verified for TNT on carbon electrodes. Limit of detection of 1.5 μmol L−1, linear range from 5 to 500 μmol L−1 and RSD lower than 4% for 10 repetitive measurements of 100 μmol L−1 TNT were obtained. The proposed devices can be reused after polishing on sandpaper generating new electrode surfaces, which is an extra advantage over chemically-modified electrochemical sensors applied for TNT detection.
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•3D pen fabricated carbon black/polylactic acid electrodes compared with 3D-printed electrodes.•Morphological analysis shows no difference, except to electrochemical surface treatment.•Highly reproducible planar three-electrode devices were fabricated (RSD = 4%, n = 5).•Similar results to those obtained on 3D-printed or screen-printed electrodes.•Application to TNT detection in a single drop (100 μL placed upon the device).
Asthma is a chronic respiratory disease produced by an aberrant immune response that originates with breathing difficulties and cough, through airway remodeling. The above pathophysiological events ...of asthma emerge the regulators of effectors, like epigenetics, which include microRNAs (miRNAs) who perform post‐transcriptional regulation, controlling diverse pathways in respiratory diseases. The objective of the study was to determine how miR‐185‐5p regulates the secretion of periostin by airway structural cells, and smooth muscle cells contraction, both related to airway remodeling in asthma. We used miR‐185‐5p mimic and inhibitors in bronchial smooth muscle cells (BSMCs) and small airway epithelial cells (SAECs) from healthy subjects. Gene expression and protein levels of periostin (POSTN), CDC42, and RHOA were analyzed by RT‐PCR and ELISA/Western blot, respectively. BSMC contractility was analyzed using cell‐embedded collagen gels and measurement of intracellular calcium was performed using Fura‐2. Additionally, miR‐185‐5p and periostin expression were evaluated in sputum from healthy and asthmatics. From these experiments, we observed that miR‐185‐5p modulation regulates periostin mRNA and protein in BSMCs and SAECs. A tendency for diminished miR‐185‐5p expression and higher periostin levels was seen in sputum cells from asthmatics compared to healthy, with an inverse correlation observed between POSTN and miR‐185‐5p. Inhibition of miR‐185‐5p produced higher BSMCs contraction induced by histamine. Calcium mobilization was not modified by miR‐185‐5p, showing that miR‐185‐5p role in BSMC contractility is performed by regulating CDC42 and RhoA pro‐contractile factors instead. In conclusion, miR‐185‐5p is a modulator of periostin secretion by airway structural cells and of smooth muscle contraction, which can be related to asthma pathophysiology, and thus, might be a promising therapeutic target.
In this study, we show that miR‐185‐5p, which is inversely correlated to POSTN expression in sputum from the asthmatic and healthy, is able to modulate periostin secretion by airway structural cells such as epithelial and smooth muscle cells, of crucial importance in airway remodeling, while also being able to regulate the synthesis of RhoA and CDC42 protein levels, which increase smooth muscle contractile capacity. These events are the key mechanisms involved in the development and maintenance of the symptoms of asthma.
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