Fabrication of an Electrically Conductive Adhesive for Skin Mounted Bioelectronic Devices

Background: Skin mounted bioelectronics are difficult to integrate with the skin since biocompatible adhesives are not conductive or unsuitable for long-term use. Skin conformability is essential but strong adhesives can damage soft tissue in younger and frail individuals as well as the device during removal. Developing a noninvasive long-lasting biocompatible conductive adhesive for skin that can be used with bioelectronics allows for better treatment options and the improvement of patient outcomes. Methods: This study creates a soft hydrogel using graphene oxide flakes (GO) and polyvinyl alcohol. Networked GO is reduced in a solution of sodium dithionite and sodium hydroxide to form a conductive network within the hydrogel. Adhesive properties are achieved by incorporating a polyacrylic acid polymer into the hydrogel with the addition of N-hydroxysulfosuccinimide (NHS) groups to the polymer. NHS reacts with amine groups found on tissue to form covalent bonds that can be released with a biocompatible trigger solution of sodium bicarbonate and glutathione. Results: Hydration of the hydrogel at 65°C demonstrated that the hydrogel swelled anistropically with swelling ratios of 1.05/1.06/5.5 (length/width/thickness). This showed that the hydrogel can integrate into various surfaces without deformation. The hydrogel demonstrated an impedance of 106.1~164.6 Ω⋅m (20~500 Hz), which is comparable to conventional devices. The hydrogel was chemically bound to amine functionalized polydimethylsiloxane (PDMS) and glass. Peel test showed peak adhesion forces of 100.5 N⋅m-1(Force⋅Width-1) when bound to PDMS or glass. Signal quality of the hydrogel showed that the hydrogels demonstrated ECG and EMG signals comparable to commercially available materials. Conclusions: The importance of this study is to create a soft material that bonds between electrodes and skin. The results demonstrate that the hydrogel has electrical characteristics comparable to conventional electrodes for use in ECG and EMG. In addition, it can create adhesion via chemical bonds that can be released on demand.

A study of the subdiffusion of small molecules in charged polyelectrolyte multilayers

A theoretical approach has been developed here to describe the slow diffusion of small charged molecules of sodium dithionite (S2O42−) in polyelectrolyte multilayers (PEMs) composed of polyallylamine hydrochloride (PAH) and polystyrene sulfonate (PSS), which is demonstrated here to be a case of subdifussion. Diffusion is measured experimentally by recording the quenching of the fluorescence of (7-nitrobenz-2-oxa-1,3-diazol-4yl) amino (NBD) labelled PAH layers assembled on silica particles by flow cytometry. NBD is reduced when it encounters dithionite leading to the disappearance of the fluorescence. The fluorescence decay curves show a slow diffusion of dithionite, that does not follow classical Fickean law. Dithionite diffusion in the PEMs is shown to be a non-Markovian process and the slow diffusion can be described via diffusion equations with fractional time derivatives. Results are explained assuming subdifussion of dithionite in the PEMs, as a result of the trapping of the negatively charged dithionite in the positively charged layers of PAH.

Thermal yellowing of hornbeam chemi-mechanical pulps bleached with hydrogen peroxide and sodium dithionite

The thermal yellowing of hornbeam chemi-mechanical pulps (CMP) after bleaching with ‎hydrogen peroxide and sodium dithionite was investigated. The hornbeam chips were randomly chosen ‎from Mazandaran wood and paper industries. The CMP pulps prepared with 85% yield were separately ‎bleached with diethylenetriamine pentaacetic acid (DTPA), without DTPA, and hydrogen ‎peroxide. Some pulps were bleached with sodium ‎dithionite. The optical ‎properties of prepared hand-sheets of 60 g/m2 after spraying with 0.5% DTPA were measured using TAPPI standard methods. All prepared papers were thermally aged ‎separately in an oven at 105 °C for 0, 10, 20, 30, and 40 h. The optical properties, such as brightness, ‎yellowness, coefficient of absorption, k/s ratio, post ‎color (PC) number, and a* factor, before and after ‎thermal aging were measured. The results showed that from 0 to 40 h, the optical properties ‎of paper increased except brightness and ‎greenness. ‎This increase was more extensive up to 15 h. Additionally, among the various treatments, DTPA treatment in long-term thermal aging and the use of ‎sodium ‎dithionite and hydrogen peroxide in the short-term aging had noticeable effects on brightness ‎‎durability and decrease in the color reversion. Thus, there was an increase in the durability of the paper ‎against thermal deterioration.

Higher Long-Term Soil Moisture Increases Organic Carbon Accrual Through Microbial Conversion of Organic Inputs

High long-term soil moisture may either stimulate or inhibit soil organic carbon (SOC) losses through changes to mineral and chemical composition, and resultant organo-mineral interactions. Yet, the trade-off between mineralization and accrual of SOC under long-term variation in unsaturated soil moisture remains an uncertainty. In this study, we tested the underexplored relationships between long-term soil moisture and organo-mineral chemical composition, and its implications for SOC persistence. The results provide new insights into SOC accrual mechanisms under different long-term moisture levels commonly observed in well-drained soils. Differences in long-term mean volumetric water content ranging from 0.4 - 0.63 (v/v) on fallow plots in an experimental field in New York, USA, were positively correlated with SOC contents (R2 = 0.228; P = 0.019, n = 20), mineral-associated organic matter (MAOM) (R2 = 0.442; P = 0.001; n = 20) and occluded particulate organic matter (oPOM) contents (R2 = 0.178; P = 0.033; n = 20). Higher long-term soil moisture decreased the relative content of sodium pyrophosphate extractable Fe (R2 = 0.33; P < 0.005; n = 20), increased that of sodium dithionite extractable Fe (R2 = 0.443; P < 0.001; n = 20), and increased the overall importance of non-crystalline Al pools (extracted with sodium pyrophosphate and hydroxylamine extractable) for SOC retention. Higher long-term soil moisture supported up to a four-fold increase in microbial biomass (per unit SOC), and lower C:N ratios in MAOM fractions of high-moisture soils (from C:N 9.5 to 9, R2 = 0.267, P = 0.011, n =20). This was reflected by a 15% and 10% greater proportion of oxidized carboxylic-C to aromatic-C and O-alkyl C, respectively, as measured with 13C-NMR, and a more pronounced FTIR signature of N-containing proteinaceous compounds in high-moisture MAOM fractions, reflective of microbial metabolites. SOC accrual increased with increasing soil moisture (P = 0.019), exchangeable Ca2+ (P = 0.013), and pyrophosphate-extractable Al content (P = 0.0001) and Al/Fe ratio (P = 0.017). Taken together, our results show that high long-term soil moisture resulted in SOC accrual by enhancing microbial conversion of plant inputs to metabolites that interact with reactive minerals.

Higher Long-Term Soil Moisture Increases Organic Carbon Accrual Through Microbial Conversion of Organic Inputs

High long-term soil moisture may either stimulate or inhibit soil organic carbon (SOC) losses through changes to mineral and chemical composition, and resultant organo-mineral interactions. Yet, the trade-off between mineralization and accrual of SOC under long-term variation in unsaturated soil moisture remains an uncertainty. In this study, we tested the underexplored relationships between long-term soil moisture and organo-mineral chemical composition, and its implications for SOC persistence. The results provide new insights into SOC accrual mechanisms under different long-term moisture levels commonly observed in well-drained soils. Differences in long-term mean volumetric water content ranging from 0.4 - 0.63 (v/v) on fallow plots in an experimental field in New York, USA, were positively correlated with SOC contents (R2 = 0.228; P = 0.019, n = 20), mineral-associated organic matter (MAOM) (R2 = 0.442; P = 0.001; n = 20) and occluded particulate organic matter (oPOM) contents (R2 = 0.178; P = 0.033; n = 20). Higher long-term soil moisture decreased the relative content of sodium pyrophosphate extractable Fe (R2 = 0.33; P < 0.005; n = 20), increased that of sodium dithionite extractable Fe (R2 = 0.443; P < 0.001; n = 20), and increased the overall importance of non-crystalline Al pools (extracted with sodium pyrophosphate and hydroxylamine extractable) for SOC retention. Higher long-term soil moisture supported up to a four-fold increase in microbial biomass (per unit SOC), and lower C:N ratios in MAOM fractions of high-moisture soils (from C:N 9.5 to 9, R2 = 0.267, P = 0.011, n =20). This was reflected by a 15% and 10% greater proportion of oxidized carboxylic-C to aromatic-C and O-alkyl C, respectively, as measured with 13C-NMR, and a more pronounced FTIR signature of N-containing proteinaceous compounds in high-moisture MAOM fractions, reflective of microbial metabolites. SOC accrual increased with increasing soil moisture (P = 0.019), exchangeable Ca2+ (P = 0.013), and pyrophosphate-extractable Al content (P = 0.0001) and Al/Fe ratio (P = 0.017). Taken together, our results show that high long-term soil moisture resulted in SOC accrual by enhancing microbial conversion of plant inputs to metabolites that interact with reactive minerals.

Azocalix[4]arene-Rhodamine Supramolecular Hypoxia-Sensitive Systems: A Search for the Best Calixarene Hosts and Rhodamine Guests

A potential hypoxia-sensitive system host-guest complex of three calixarenes (including two with four anionic carboxyl and sulphonate azo fragments on the upper rim and a newly synthesized bis-azo adduct of calixarene in the cone configuration with azo fragments on the lower rim with the most widespread cationic and zwitterionic rhodamine dyes (123, 6G and B)) was studied using UV-VIS spectrometry and fluorescence as well as 1D and 2D NMR techniques. It was found that all three calixarenes form a complex with rhodamine dyes with a 1:1 composition. The association constants of calixarene-dye complexes with sulfonate calixarenes, especially in the case of tetra-anionic calixarene, turned out to be higher compared with carboxyl calixarene due to the more intense electrostatic interactions. For the first time using an HRESI MS technique, it was shown that the treatment of rhodamine 6G and 123 with sodium dithionite (SDT) produces a non-fluorescent leuco form of the dye, and only rhodamine B can be used with SDT without the occurrence of a side reduction. Moreover, it was identified that in addition to the reduction in the azo groups, SDT causes partial cleavage of the aryl ether bonds. The found features of SDT should be taken into account when SDT is used as an azoreductase mimic.

Magnetophoretic and spectral characterization of oxyhemoglobin and deoxyhemoglobin: Chemical versus enzymatic processes

A new method for hemoglobin (Hb) deoxygenation, in suspension or within red blood cells (RBCs) is described using the commercial enzyme product, EC-Oxyrase®. The enzymatic deoxygenation method has several advantages over established deoxygenation methodologies, such as avoiding side reactions that produce methemoglobin (metHb), thus eliminating the need for an inert deoxygenation gas and airtight vessel, and facilitates easy re-oxygenation of Hb/RBCs by washing with a buffer that contains dissolved oxygen (DO). The UV-visible spectra of deoxyHb and metHb purified from human RBCs using three different preparation methods (sodium dithionite [to produce deoxyHb], sodium nitrite [to produce metHb], and EC-Oxyrase® [to produce deoxyHb]) show the high purity of deoxyHb prepared using EC-Oxyrase® (with little to no metHb or hemichrome production from side reactions). The oxyHb deoxygenation time course of EC-Oxyrase® follows first order reaction kinetics. The paramagnetic characteristics of intracellular Hb in RBCs were compared using Cell Tracking Velocimetry (CTV) for healthy and sickle cell disease (SCD) donors and oxygen equilibrium curves show that the function of healthy RBCs is unchanged after EC-Oxyrase® treatment. The results confirm that this enzymatic approach to deoxygenation produces pure deoxyHb, can be re-oxygenated easily, prepared aerobically and has similar paramagnetic mobility to existing methods of producing deoxyHb and metHb.

Synthesis of Unsymmetrically Functionalized Violanthrenes by Reductive Aromatization of Violanthrone 79

The commercially available n-type semiconductive dye Violanthrone 79 is used as starting material to synthesize via a reductive aromatization and functionalization strategy so far unexplored substituted violanthrenes. Using the low-cost reducing agents zinc and sodium dithionite in combination with suitable electrophilic trapping reagents, three violanthrenes functionalized with two pivalyloxy, trimethylsiloxy or methoxy groups are selectively obtained in high yields. Due to their octyl ether moieties, these new red dyes are highly soluble. They are characterized by means of UV-Vis and fluorescence spectroscopy and their redox properties are studied via cyclic voltammetry. The spectroscopically determined frontier molecular orbital energies are compared to those calculated by density functional theory and suggest, that electron-poor Violanthrone 79 was transformed into electron-rich violonthrenes VE1-VE3 with molecular characteristics typically observed in molecular precursors for p-type organic semiconductors.