3D-printed holder for drawing highly reproducible pencil-on-paper electrochemical devices.

Pencil drawing is one of the simplest and most cost-effective ways of fabricating miniaturized electrodes on a paper substrate. However, it is limited by the lack of reproducibility regarding the electrode drawing process. A 3D-printed pencil holder (3DPH) is proposed here for simple, reproducible, and low-cost hand-drawn fabrication of paper-based electrochemical devices. 3DPH was designed to keep pressure and angulation of the graphite mine constant on the paper substrate using a micromechanical pencil regardless of the user/operator. This approach significantly improved the reproducibility and cost of making reliable pencil-drawn electrodes. The results showed high reproducibility and accuracy of the 3DPH-assisted electrodes prepared by 4 different operators in terms of sheet resistance and electrochemical behavior. Cyclic voltammetric (CV) curves in the presence of [Fe(CN)6]3-/4- redox probe showed only 3.9% variation for the anodic peak currents of different electrodes prepared by different operators when compared with electrodes prepared without the 3D-printed support. SEM analyses revealed a more uniform graphite deposition/design of the electrodes prepared with 3DPH, which corroborates the results obtained by CV. As a proof of concept, 3DPH-assisted pencil-drawn graphite electrodes were employed for dopamine detection in synthetic saliva, showing a proportional increase in anodic peak current at 0.12 V vs. carbon pRE with increasing dopamine (DA) concentration, with a detection limit of 0.39µmol L-1. Moreover recovery was in the range 93-104% of DA (4-7% RSD) in synthetic saliva for three different concentrations, demonstrating the reliability of the approach. Finally, we believe this approach can make pencil-drawn technology more robust, accessible, reliable, and inexpensive for real on-site applications, especially in hard-to-reach locations or research centers with little investment.

Corrigendum to "A novel approach for electroanalytical determinations employing discharge of pseudocapacitor by electroactive species" [Analytica Chimica Acta 1006 (2018) 1-9].

The purpose of this Corrigendum is to cite and comment on an important reference that brings some support to the ideas developed in this paper and should be chronologically inserted into the history of advances in this area.

A novel approach for electroanalytical determinations employing discharge of pseudocapacitor by electroactive species.

In this paper, we introduce a novel approach for the detection of electroactive analytes by using oxidant species accumulated in pseudocapacitors surface. We demonstrated that pseudocapacitors can be quickly discharged when in contact with electroactive species. Thus, the variation of potential can be monitored during the discharging process and correlated with the analyte concentration. Based on this, two electroanalytical methods were proposed: continuous discharging detection and pulsed discharging detection. As a proof of concept, these methods were employed for glucose, fructose and sucrose detection using an ion chromatograph containing an electrochemical detector. Copper|cupric oxide in alkaline medium was used as the pseudocapacitive system. The obtained results proved to be very promising and the analytical curves showed good linearity in both methods. In addition, this novel approach for the detection of saccharides based on potential variation as a result of the discharging of the pseudocapacitor in contact with the analyte is very attractive because it does not require current reading. Therefore, our approach can be applied to other pseudocapacitive systems, opening new possibilities for several electroanalytical applications.

Insight into the Electro-Oxidation Mechanism of Glucose and Other Carbohydrates by CuO-Based Electrodes.

In this work, a new hypothesis for the electrocatalytic behavior of CuO electrodes is presented. Different from the established mechanism, here we discuss why CuIII species do not participate in the oxidation mechanism of carbohydrates. We show that hydroxyl ion adsorption and the semiconductive properties of the material play a more significant role in this process. The relationship between the flat band potential and the potential that begin oxidation suggests that the concentration of vacancies in the charge region acts upon the reactivity of the adsorbed hydroxyl ions through a partial charge transfer reaction. In the presence of carbohydrate molecules, the electron transfer is facilitated and involves the transfer of electrons from the adsorbed hydroxyl ions to the CuO film. This mechanism is fundamentally relevant since it helps the understanding of several experimental misleads. The results can also lead to obtaining better catalysts, since improvements in the material should focus on enhancing the semiconductive properties rather than the CuII/CuIII redox transition. The results shed light on different aspects of carbohydrate molecules oxidation that could lead to novel applications and possibly a better description of other semiconductor mechanisms in electrocatalysis.

Microwave-assisted synthesis of palladium nanoparticles intercalated nitrogen doped reduced graphene oxide and their electrocatalytic activity for direct-ethanol fuel cells.

Palladium nanoparticles decorated reduced graphene oxide (Pd-rGO) and palladium nanoparticles intercalated inside nitrogen doped reduced graphene oxide (Pd-NrGO) hybrids have been synthesized by applying a very simple, fast and economic route using microwave-assisted in-situ reduction and exfoliation method. The Pd-NrGO hybrids materials show good activity as catalyst for ethanol electro oxidation for direct ethanol fuel cells (DEFCs) as compared to Pd-rGO hybrids. The enhanced direct ethanol fuel cell can serve as alternative to fossil fuels because it is renewable and environmentally-friendly with a high energy conversion efficiency and low pollutant emission. As proof of concept, the electrocatalytic activity of Pd-NrGO hybrid material was accessed by cyclic voltammetry in presence of ethanol to evaluate its applicability in direct-ethanol fuel cells (DEFCs). The Pd-NrGO catalyst presented higher electro active surface area (∼6.3 m2 g-1) for ethanol electro-oxidation when compared to Pd-rGO hybrids (∼3.7 m2 g-1). Despite the smaller catalytic activity of Pd-NrGO, which was attributed to the lower exfoliation rate of this material in relation to the Pd-rGO, Pd-NrGO showed to be very promising and its catalytic activity can be further improved by tuning the synthesis parameters to increase the exfoliation rate.

Direct laser writing of micro-supercapacitors on thick graphite oxide films and their electrochemical properties in different liquid inorganic electrolytes.

In this article we demonstrate a simple approach to fabricate interdigitated in-plane electrodes for flexible micro-supercapacitors (MSCs). A nanosecond ultraviolet laser treatment is used to reduce and pattern the electrodes on thick graphite oxide (GO) freestanding films. These laser-treated regions obtained by direct writing provide the conducting channels for electrons in the capacitors. The electrochemical performance of the MSCs was evaluated in the presence of two different electrolytes and they exhibit characteristics of nearly electrical double layer capacitors. The MSCs have areal capacitances as 2.40, 2.23 and 1.62µF/cm2 for NaOH, Na2SO4 and KCl electrolytes respectively, for measurements performed at the scan rate of 50mV/s. They retain ∼93.1% of their initial capacitances after 3500 cycles (scan rate=80mV/s) in NaOH electrolyte. The proposed laser treatment approach enables facile and fast fabrication of flexible MSCs without the need for tedious processing methods such as photolithographic micro-patterning and deposition of porous carbon or metallic current collectors.

Association of season of birth with DNA methylation and allergic disease.

BACKGROUND: Season of birth influences allergy risk; however, the biological mechanisms underlying this observation are unclear. The environment affects DNA methylation, with potentially long-lasting effects on gene expression and disease. This study examined whether DNA methylation could underlie the association between season of birth and allergy. METHODS: In a subset of 18-year-old participants from the Isle of Wight (IoW) birth cohort (n = 367), the risks of birth season on allergic outcomes were estimated. Whole blood epigenome-wide DNA methylation was measured, and season-associated CpGs detected using a training-and-testing-based technique. Validation method examined the 8-year-old Prevention and Incidence of Asthma and Mite Allergy (PIAMA) cohort. The relationships between DNA methylation, season of birth and allergy were examined. CpGs were analysed in IoW third-generation cohort newborns. RESULTS: Autumn birth increased risk of eczema, relative to spring birth. Methylation at 92 CpGs showed association with season of birth in the epigenome-wide association study. In validation, significantly more CpGs had the same directionality than expected by chance, and four were statistically significant. Season-associated methylation was enriched among networks relating to development, the cell cycle and apoptosis. Twenty CpGs were nominally associated with allergic outcomes. Two CpGs were marginally on the causal pathway to allergy. Season-associated methylation was largely absent in newborns, suggesting it arises post-natally. CONCLUSIONS: This study demonstrates that DNA methylation in adulthood is associated with season of birth, supporting the hypothesis that DNA methylation could mechanistically underlie the effect of season of birth on allergy, although other mechanisms are also likely to be involved.

Identifying CpG sites associated with eczema via random forest screening of epigenome-scale DNA methylation.

BACKGROUND: The prevalence of eczema is increasing in industrialized nations. Limited evidence has shown the association of DNA methylation (DNA-M) with eczema. We explored this association at the epigenome-scale to better understand the role of DNA-M. Data from the first generation (F1) of the Isle of Wight (IoW) birth cohort participants and the second generation (F2) were examined in our study. Epigenome-scale DNA methylation of F1 at age 18 years and F2 in cord blood was measured using the Illumina Infinium HumanMethylation450 Beadchip. A total of 307,357 cytosine-phosphate-guanine sites (CpGs) in the F1 generation were screened via recursive random forest (RF) for their potential association with eczema at age 18. Functional enrichment and pathway analysis of resulting genes were carried out using DAVID gene functional classification tool. Log-linear models were performed in F1 to corroborate the identified CpGs. Findings in F1 were further replicated in F2. RESULTS: The recursive RF yielded 140 CpGs, 88 of which showed statistically significant associations with eczema at age 18, corroborated by log-linear models after controlling for false discovery rate (FDR) of 0.05. These CpGs were enriched among many biological pathways, including pathways related to creating transcriptional variety and pathways mechanistically linked to eczema such as cadherins, cell adhesion, gap junctions, tight junctions, melanogenesis, and apoptosis. In the F2 generation, about half of the 83 CpGs identified in F1 showed the same direction of association with eczema risk as in F1, of which two CpGs were significantly associated with eczema risk, cg04850479 of the PROZ gene (risk ratio (RR) = 15.1 in F1, 95 % confidence interval (CI) 1.71, 79.5; RR = 6.82 in F2, 95 % CI 1.52, 30.62) and cg01427769 of the NEU1 gene (RR = 0.13 in F1, 95 % CI 0.03, 0.46; RR = 0.09 in F2, 95 % CI 0.03, 0.36). CONCLUSIONS: Via epigenome-scaled analyses using recursive RF followed by log-linear models, we identified 88 CpGs associated with eczema in F1, of which 41 were replicated in F2. Several identified CpGs are located within genes in biological pathways relating to skin barrier integrity, which is central to the pathogenesis of eczema. Novel genes associated with eczema risk were identified (e.g., the PROZ and NEU1 genes).

Triboelectric effect as a new strategy for sealing and controlling the flow in paper-based devices.

We reported here for the first time that triboelectric charges on PET sheets can be used to seal and control the flow rate in paper-based devices. The proposed method exhibits simplicity and low cost, provides reversible sealing and minimizes the effect of sample evaporation.

High potassium diets reduce vascular and plasma lipid peroxides in stroke-prone spontaneously hypertensive rats.

We examined the effect of high potassium (K) diet on oxidative stress to endothelium in hypertensive rats. Five-week-old stroke-prone spontaneously hypertensive rats (SHRsp) were fed a 5% high NaCl diet containing either 0.5% normal K (n = 28) or 2.1% high K (n = 19) for 6 weeks, and lipid peroxides in the aortic intima and plasma were measured. Lipid peroxides were extracted into an organic solvent to avoid the interference of carbohydrates or glycoproteins, and malondialdehyde (MDA) produced from lipid peroxides by acid-heating was measured by its reaction to thiobarbituric acid. The antioxidant butylated hydroxytoluene prevented spurious lipid peroxide formation during the whole procedure, and optimum Fe3+ allowed a maximum MDA production from lipid peroxides. The high K SHRsp showed lower lipid peroxide levels than the normal K SHRsp both in the intima (5.6 +/- 0.3 vs. 7.2 +/- 0.4 nmol MDA/mg fatty acids, p < 0.003) and plasma (0.91 +/- 0.08 vs. 1.46 +/- 0.10 nmol MDA/ml, p < 0.001). Mean arterial pressure was slightly lower by 13 mmHg in the high K SHRsp, but these differences were still obvious even when we compared groups of rats with precisely matching blood pressures. These results indicate that high K diets reduce oxidative stress on the endothelium of high NaCl-fed SHRsp independently of blood pressure changes. This effect may be involved in the mechanism by which high K diets protect endothelium and reduce stroke incidence in hypertensive animals. Thus, we improved the method of lipid peroxide measurement and propose the protective effects of high K diet against oxidative stress to endothelium in hypertension animals.

Analysis of CA repeat polymorphisms places three human gene loci on the 8p linkage map.

The gene loci for luteinizing hormone-releasing hormone (LHRH), the beta-3 adrenergic receptor (ADRB3), and heregulin (HGL) have been assigned to the short arm of human chromosome 8, but the positions of these loci on the human genetic linkage map have not been previously reported. We have isolated simple tandem repeat polymorphisms (STRPs) for these loci. These STRPs enabled us to determine the genetic map locations for these genes.

Factors affecting herd milk composition and milk plasmin at four levels of somatic cell counts.

A longitudinal study was carried out on samples of bulk tank milk collected from 200 farms for 12 mo to evaluate SCC, plasmin and plasminogen activities, psychrotrophic bacteria count, and protein quality in milk and to examine the proteolytic effects of plasmin on milk proteins. Herds were selected randomly from client lists of two dairies to create four groups based on milk SCC of the month before the study; herds were reassigned monthly to one of four groups based on SCC for that month. Overall means were 3.73% fat, 3.13% protein by infrared analysis, 3.16% protein by Kjeldahl analysis, 2.42% casein percentage, 4.65% lactose, 5.43 cells/ml of log SCC, 1.13 U of plasmin, 45.6 U of plasminogen, and log 2.86 cfu/ml of psychrotrophic bacteria. The ANOVA showed a significant effect of month on all factors except SCC, which was fixed by the experimental design. Plasmin and plasminogen activities were high from December to May. Plasmin activities and psychrotroph counts were significantly higher for the high SCC group. Casein percentage and number were significantly higher for the low SCC group.

Industry response to the problems of pathogenic bacteria.

An on-farm assessment of sources of pathogenic bacteria in milk will be presented. Control of pathogenic bacteria through on-farm sanitation and herd management programs are part of the presentation. The processing plant environment and controls enacted in response to the menace of emerging pathogens will be reviewed. The current status of pathogen incidence and sources in dairy plants as evidenced by surveys provided by national trade organizations will also be presented.

Pressure-reduction limits for rats following steady-state exposures between 6 and 60 ATA.

The role of pressure reduction in the formation and growth of bubbles is universally recognized and its significance in decompression theory has been accepted. Yet the allowable limits of pressure reduction for man and animal are uncertain. This study sought to evaluate the pressure-reduction limits for rats following steady-state exposures at pressures greater than 1 atm. To define the relationship, 350 albino rats were exposed to 1 of 12 specified pressure levels between 6 and 60 ATA and then abruptly decompressed to a preselected reduced pressure level for observation. The pressure-reduction levels were selected to determine for each saturation-exposure level an ED-50 (i.e. the effective dose that will produce decompression sickness in 50% of the animals). The results demonstrate three consistent findings: (1) there is a linear relationship (r = .99) between the magnitude of a safe pressure reduction and the saturation exposures between 6 and 43 ATA; (2) at pressures greater than 43 ATA, there is a qualitative change in the decompression sickness symptoms and a reduction in the precision of the mathematical relationship (r = .44); and (3) the magnitude of the pressure change required to increase the incidence of decompression sickness from 10% to 90% is directly related to the magnitude of the exposure pressure. The implications of these results for deep operational diving are discussed.