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At least 19 records

Different Electrochemical Behavior of Cationic Dopamine from Anionic Ascorbic Acid and DOPAC at CNT Yarn Microelectrodes

Carbon nanotube yarn microelectrodes (CNTYMEs) have micron-scale surface crevices that momentarily trap molecules. CNTYMEs improve selectivity among cationic catecholamines because secondary reactions are enhanced, but no anions have been studied. Here, we compared fast-scan cyclic voltammetry (FSCV) of dopamine and anionic interferents 3,4 dihydroxyphenylacetic acid (DOPAC) and L-ascorbic acid (AA) at CNTYMEs and carbon fiber microelectrodes (CFMEs). At CFMEs, dopamine current decreases with increasing FSCV repetition frequency at pH 7.4, whereas DOPAC and AA have increasing currents with increasing frequency, because of less repulsion at the negative holding potential. Both DOPAC and AA have side reactions after being oxidized, which are enhanced by trapping. At pH 4, the current increases for DOPAC and AA because they are not repelled. In addition, AA has a different oxidation pathway at pH 4, and an extra peak in the CV is enhanced by trapping effects at CNTYMEs. At pH 8.5, co-detection of dopamine in the presence of DOPAC and AA is enhanced at 100 Hz frequency because of differences in secondary peaks. Thus, the trapping effects at CNTYMEs affects anions differently than cations and secondary peaks can be used to identify dopamine in mixture of AA and DOPAC with FSCV.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ascorbic Acid Stability and pH Testing to Support RWM-018 Pilot Scale Wellhead Treatment System Feasibility Determination

A multitude of groundwater remediation techniques for chlorinated volatile organic compounds (cVOCs) have been conducted at the A/M-Areas of the Savannah River Site (SRS). Historical in-situ chemical oxidation (ISCO) injections of potassium permanganate and sodium persulfate conducted in 2018 and 2020, have left residual oxidant concentrations in the A/M-Area groundwater system. ISCO events targeted dense non-aqueous phase liquids (DNAPLs) through the injection of strong oxidants within plume zones upgradient of current groundwater recovery wells RWM-008 and RWM-018. These residual oxidants could significantly impede the operation of the mercury removal system needed to meet National Pollutant Discharge Elimination System (NPDES) permit requirements for the ongoing pump-and-treat system that hydraulically controls potions of the A/M-Area plume. Effluent treated groundwater from this system is discharged to surface water at the receiving outfall of the M-1 Air Stripper. To prevent interference of the M-1 Air Stripper system by residual oxidants, groundwater recovery has been ceased at well RWM-018. Modeling of oxidant transport in A/M-Area from ISCO estimated that the potential oxidant load contributed by RWM-018 could be as high as 120 mg/L. It is also possible that oxidants may be contributed via pumping at well RWM-008 in the near future as residual oxidants within the aquifer migrate toward its zone of influence. Savannah River National Laboratory (SRNL) has conducted research to investigate potential pre-treatment chemicals to neutralize these residual oxidants, before reaching the M-1 Air Stripper, to allow for resumed groundwater recovery at RWM-018 and continued pumping at RWM-008. Deployment of ascorbic acid for neutralization of residual oxidants at RWM-018 (and possibly RWM-008) is recommended based on results from previous reductant testing (SRNL, 2021). For a maximum estimated oxidant load at RWM-0018, a well-head treatment system would need to dose about 400 gallons of ascorbic acid each month to ensure complete neutralization. A second system with additional reagent should also be considered for deployment at RWM-008.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

High-Performance Piezo-Electrocatalytic Sensing of Ascorbic Acid with Nanostructured Wurtzite Zinc Oxide

We report nanostructured piezoelectric semiconductors offer unprecedented opportunities for high-performance sensing in numerous catalytic processes of biomedical, pharmaceutical, and agricultural interests, leveraging piezocatalysis that enhances the catalytic efficiency with the strain-induced piezoelectric field. Here, we design and demonstrate for the first time a cost-efficient, high-performance piezo-electrocatalytic sensor for detecting L-ascorbic acid (AA), a critical chemical for many organisms, metabolic processes, and medical treatments. We prepared ZnO nanorods and nanosheets to characterize and compare their efficacy for the piezo-electrocatalysis of AA. The electrocatalytic efficacy of AA was significantly boosted by the piezoelectric polarization induced in the nanostructured semiconducting ZnO catalysts. We elucidated the charge transfer between the strained ZnO nanostructures and AA to reveal the mechanism for the related piezo-electrocatalytic process. The low-temperature synthesis of high-quality ZnO nanostructures allows the low-cost, scalable production and integration directly into wearable electrocatalytic sensors whose performance could be boosted by otherwise wasted mechanical energy from the working environment, e.g., the human-generated mechanical signals.

30 DIRECT ENERGY CONVERSION↗

Osteoblastic phenotype of rat marrow stromal cells cultured in the presence of dexamethasone, beta-glycerolphosphate, and L-ascorbic acid

We investigated the effects of the time course of addition of osteogenic supplements dexamethasone, beta-glycerolphosphate, and L-ascorbic acid to rat marrow stromal cells, and the exposure time on the proliferation and differentiation of the cells. It was the goal of these experiments to determine the time point for supplement addition to optimize marrow stromal cell proliferation and osteoblastic differentiation. To determine this, two studies were performed; one study was based on the age of the cells from harvest, and the other study was based on the duration of exposure to supplemented medium. Cells were seen to proliferate rapidly at early time points in the presence and absence of osteogenic supplements as determined by 3H-thymidine incorporation into the DNA of replicating cells. These results were supported by cell counts ascertained through total DNA analysis. Alkaline phosphatase (ALP) activity and osteocalcin production at 21 days were highest for both experimental designs when the cells were exposed to supplemented medium immediately upon harvest. The ALP levels at 21 days were six times greater for cells maintained in supplements throughout than for control cells cultured in the absence of supplements for both studies, reaching an absolute value of 75 x 10(-7) micromole/min/cell. Osteocalcin production reached 20 x 10(-6) ng/cell at 21 days in both studies for cells maintained in supplemented medium throughout the study, whereas the control cells produced an insignificant amount of osteocalcin. These results suggest that the addition of osteogenic supplements to marrow-derived cells early in the culture period did not inhibit proliferation and greatly enhanced the osteoblastic phenotype of cells in a rat model.

Non-NASA Center↗

Study on the effect of ascorbic acid on the biosynthesis of pigment and citrinin in red yeast rice based on comparative transcriptomics

Pigment is one of the most important metabolites in red yeast rice. However, citrinin may accumulate and cause quality security issues. In the present study, the effect of ascorbic acid (EAA) on the pigment and citrinin was studied, and the metabolic mechanism was discussed using comparative transcriptomics. The introduction of EAA increased the pigment by 58.2% and decreased citrinin by 65.4%. The acid protease activity, DPPH scavenging rate, and total reducing ability also increased by 18.7, 9.0, and 26.7%, respectively. Additionally, a total of 791 differentially expressed genes were identified, and 79 metabolic pathways were annotated, among which carbon metabolism, amino acid metabolism, and fatty acid metabolism were closely related to the biosynthesis of pigment and citrinin. Ethanol dehydrogenase ( M pigC ), oxidoreductase ( M pigE ), reductase ( M pigH ), and monooxygenase ( M pigN ) may be related to the increase of pigment. ctnC and pksCT contributed to the decline of citrinin.

Jiang, Zhilin↗

Hole-scavenging in photo-driven N 2 reduction catalyzed by a CdS-nitrogenase MoFe protein biohybrid system

The light-driven reduction of dinitrogen (N 2 ) to ammonia (NH 3 ) catalyzed by a cadmium sulfide (CdS) nanocrystal-nitrogenase MoFe protein biohybrid is dependent on a range of different factors, including an appropriate hole-scavenging sacrificial electron donor (SED). Here, the impact of different SEDs on the overall rate of N 2 reduction catalyzed by a CdS quantum dot (QD)-MoFe protein system was determined. The selection of SED was guided by several goals: (i) molecules with standard reduction potentials sufficient to reduce the oxidized CdS QD, (ii) molecules that do not absorb the excitation wavelength of the CdS QD, and (iii) molecules that could be readily reduced by sustainable processes. Earlier studies utilized buffer molecules or ascorbic acid as the SED. The effectiveness of ascorbic acid as SED was compared to dithionite (DT), triethanolamine (TEOA), and hydroquinone (HQ) across a range of concentrations in supporting N 2 reduction to NH 3 in a CdS QD-MoFe protein photocatalytic system. It was found that TEOA supported N 2 reduction rates comparable to those observed for dithionite and ascorbic acid. HQ was found to support significantly higher rates of N 2 reduction compared to the other SEDs at a concentration of 50 mM. A comparison of the rates of N 2 reduction by the biohybrid complex to the standard reduction potential (E o ) of the SEDs reveals that E o is not the only factor impacting the efficiency of hole-scavenging. These findings reveal the importance of the SED properties for improving the efficiency of hole-scavenging in the light-driven N 2 reduction reaction catalyzed by a CdS QD–MoFe protein hybrid.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ingeniously enhanced ferromagnetism in chemically-reduced 2D Ti 3 C 2 T X MXene

Chemical reduction is a facile and cost-effective technique for the modulation of the physical and chemical properties of nanomaterials. In this work, we demonstrate an enhancement of the magnetic behavior of Ti 3 C 2 T x MXene after its chemical reduction via l-ascorbic acid treatment. Small ferromagnetic loops have been observed below 50 K for Ti 3 C 2 T x prepared by hydrofluoric acid (HF) etching of Al layers from Ti 3 AlC 2 . Such a ferromagnetic ordering of spins was significantly enhanced via a chemical reduction of Ti 3 C 2 T x with l-ascorbic acid. Ferromagnetic hysteresis loops were observed for reduced Ti 3 C 2 T x (r-Ti 3 C 2 T x ) up to 150 K indicating a significant upshift of the paramagnetic to the ferromagnetic transition temperature, pushing towards room temperature. The enhancement of ferromagnetism and upshift of the ferromagnetic transition temperature could be attributed to the localized unpaired electron in Ti-3d orbital of the r-Ti 3 C 2 T x crystal and increase in the number of unsaturated Ti atoms upon l-ascorbic acid treatment. Chemical reduction via l-ascorbic acid treatment shows a promising pathway towards the modulation and enhancement of magnetism in various MXene materials for the development of 2D metallic soft ferromagnets and spintronic devices.

36 MATERIALS SCIENCE↗

Microencapsulation of methylglyoxal and two derivatives

Microcapsules of methylglyoxal, methylglyoxal bis(guanylhydrazone), and methylglyoxal-ascorbic acid condensation complex were prepared and release curves were determined. The effect of various concentrations of hydrochloric acid on the decomposition of the ascorbic acid complex was investigated.

Nozawa, Y.↗

Regulation of collagenase-3 and osteocalcin gene expression by collagen and osteopontin in differentiating MC3T3-E1 cells

Both collagenase-3 and osteocalcin mRNAs are expressed maximally during the later stages of osteoblast differentiation. Here, we demonstrate that collagenase-3 mRNA expression in differentiating MC3T3-E1 cells is dependent upon the presence of ascorbic acid, is inhibited in the presence of the collagen synthesis inhibitor, 3,4-dehydroproline, and is stimulated by growth on collagen in the absence of ascorbic acid. Transient transfection studies show that collagenase-3 promoter activity increases during cell differentiation and requires the presence of ascorbic acid. Additionally, we show that, in differentiating MC3T3-E1 cells, collagenase-3 gene expression increases in the presence of an anti-osteopontin monoclonal antibody that binds near the RGD motif of this protein, whereas osteocalcin expression is inhibited. Furthermore, an RGD peptidomimetic compound, designed to block interaction of ligands to the alpha(v) integrin subunit, increases osteocalcin expression and inhibits collagenase-3 expression, suggesting that the RGD peptidomimetic initiates certain alpha(v) integrin signaling in osteoblastic cells. Overall, these studies demonstrate that stimulation of collagenase-3 expression during osteoblast differentiation requires synthesis of a collagenous matrix and that osteopontin and alpha(v) integrins exert divergent regulation of collagenase-3 and osteocalcin expression during osteoblast differentiation.

NASA Discipline Musculoskeletal↗

Influence of QD photosensitizers in the photocatalytic production of hydrogen with biomimetic [FeFe]-hydrogenase. Comparative performance of CdSe and CdTe

Photocatalytic systems comprising a hydrogenase-type catalyst and CdX (X = S, Se, Te) chalcogenide quantum dot (QD) photosensitizers show extraordinary hydrogen production rates under visible light excitation. What remains unknown is the mechanism of energy conversion in these systems. In this work, we have explored this question by comparing the performance of two QD sensitizers, CdSe and CdTe, in photocatalytic systems featuring aqueous suspensions of a [Fe 2 (μ-1,2-benzenedithiolate) CO 6 ] catalyst and an ascorbic acid sacrificial agent. Overall, the hydrogen production yield for CdSe-sensitized reactions QDs was found to be 13 times greater than that of CdTe counterparts. According to emission quenching experiments, an enhanced performance of CdSe sensitizers reflected a greater rate of electron transfer from the ascorbic acid (k Asc ). The observed difference in the QD-ascorbic acid charge transfer rates between the two QD materials was consistent with respective driving forces for these systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Kinetic and Thermodynamic Characterization of the Cobalt and Manganese Oxyhydroxide Cores Formed in Horse Spleen Ferritin

Horse spleen ferritin (HoSF) containing 800-1500 cobalt or 250-1200 manganese atoms as Co(O)OH and Mn(O)OH mineral cores within the HoSF interior (Co-HoSF and Mn-HoSF) was synthesized, and the chemical reactivity, kinetics of reduction, and the reduction potentials were measured. Microcoulometric and chemical reduction of HoSF containing the M(O)OH mineral core (M = Co or Mn) was rapid and quantitative with a reduction stoichiometry of 1.05+/-0.10 e/M forming a stable M(OH)2 mineral core. At pH 9.0, ascorbic acid (AH2), a two-electron reductant, effectively reduced the mineral cores; however, the reaction was incomplete and rapidly reached equilibrium. The addition of excess AH2 shifted the reaction to completion with a M(3+)/AH2 stoichiometry of 1.9-2.1, consistent with a single electron per metal atom reduction. The rate of reaction between M(0)OH and excess AH2 was measured by monitoring the decrease in mineral core absorbance with time. The reaction was first order in each reactant with second-order rate constants of 0.53 and 4.74/M/min, respectively, for Co- and Mn-HoSF at pH 9.0. From the variation of absorbance with increasing AH2 concentration, equilibrium constants at pH 9.0 of 5.0+/-1.9 for Co-HoSF and 2.9+/-0.9 for Mn-HoSF were calculated for 2M(O)OH + AH2 = 2M(OH)2 f D, where AH2 and D are ascorbic acid and dehydroascorbic acid, respectively. Consistent with these equilibrium constants, the standard potential for the reduction of Co(III)-HoSF is 42 mV more positive than that of the ascorbic acid reaction, while the standard potential of Mn(III)-HoSF is 27 mV positive relative to AH2. Fe(2+) in solution with Co- and Mn-HoSF under anaerobic conditions was oxidized to form Fe(O)OH within the HoSF interior, resulting in partial displacement of the Co or Mn by iron.

Zhang, Bo↗

A Sorghum F-Box Protein Induces an Oxidative Burst in the Defense Against Colletotrichum sublineola

The hemibiotrophic fungal pathogen Colletotrichum sublineola is the causal agent of anthracnose in sorghum ( Sorghum bicolor), resulting in leaf blight, stalk rot, and head blight in susceptible genotypes, with yield losses of up to 50%. The development of anthracnose-resistant cultivars can reduce reliance on fungicides and provide a more sustainable and economical means for disease management. A previous genome-wide association study of the sorghum association panel identified the candidate resistance gene Sobic.005G172300 encoding an F-box protein. To better understand the role of this gene in the defense against C. sublineola, gene expression following infection with C. sublineola was monitored by RNA sequencing in seedlings of sorghum accession SC110, which harbored the resistance allele, and three accessions that harbored a susceptible allele. Only in SC110 did the expression of Sobic.005G172300 increase during the biotrophic phase of infection. Subsequent transcriptome analysis, gene co-expression networks, and gene regulatory networks of inoculated and mock-inoculated seedlings of resistant and susceptible accessions suggest that the increase in expression of Sobic.005G172300 induces an oxidative burst by lowering the concentration of ascorbic acid during the biotrophic phase of infection. Based on gene regulatory network analysis, the protein encoded by Sobic.005G172300 is proposed to target proteins involved in the biosynthesis of ascorbic acid for polyubiquitination through the SCF E3 ubiquitin ligase, causing their degradation via the proteasome.

Plant Sciences↗