Mediated Electrochemistry to Mimic Biology's Oxidative Assembly of Functional Matrices

Biology uses diffusible oxidants to perform functions that range from signaling to matrix assembly, and these oxidation chemistries offer surprising selectivities. Here, it is reported that mediated electrochemistry can access the richness of such oxidation chemistries. Specifically, electrode‐imposed voltage inputs are used to locally generate oxidized mediators that can diffuse into polymer solutions and induce the formation of covalent bonds for the deposition and functionalization of hydrogels at the electrode surface. Depending on the mediator's redox potential (E⁰), it is possible to “gate” the voltage inputs to target specific residues (e.g., thiols or amines) and oxidation chemistries. Further, mediators of varying E⁰ offer different reactivities and thus allow control of reaction‐diffusion rates to modulate the hydrogel's crosslink density and mechanical properties. Importantly, this mediated oxidation can be performed under physiologically relevant conditions to preserve labile biological functionalities (e.g., cell viability and protein function). Finally, it is demonstrated that protein fusion tags can be engineered to have “targetable” amino acid residues that enable protein function to be oxidatively conjugated to electrodeposited hydrogels. In summary, mediated electrochemistry can engage orthogonal oxidation chemistries to create functionalized matrices and thus mediated electrochemistry should add important capabilities to the electrofabrication toolbox.     

Characterization of Pt?CAu and Ni?CAu Clusters on TiO2(110)

The surface composition and properties of Pt?CAu and Ni?CAu clusters on TiO₂(110) have been studied by scanning tunneling microscopy (STM), low energy ion scattering (LEIS) and soft X-ray photoelectron spectroscopy (sXPS). STM studies show that bimetallic clusters are formed during sequential deposition of the two metals, regardless of the order of deposition. At the 2?ML of Au/2?ML of Pt or Ni coverages studied here, the second metal contributes to the growth of existing clusters rather than forming new pure metal clusters. LEIS experiments demonstrate that the surfaces of the bimetallic clusters are almost 100% Au when 2?ML of Au is deposited on top of 2?ML of Pt or Ni. However, a much larger fraction of Pt or Ni (50 and 20%, respectively) remains at the surface when 2?ML of Pt or Ni is deposited on 2?ML of Au, most likely due to limited diffusion of atoms within the clusters at room temperature. According to sXPS investigations, the binding energies of the metals in the bimetallic clusters are shifted from those observed for pure metal clusters; the Pt(4f_7/2) and Ni(3p_3/2) peaks are shifted to lower binding energies while the position of the Au(4f_7/2) peak is dominated by surface core level shifts. Pure Pt clusters as well as 0.4?ML of Au on 2 ML of Pt clusters reduce the titania support upon encapsulation after annealing to 800?K, whereas 2?ML of Au on 2?ML of Pt clusters do not reduce titania, presumably because there is no Pt at the surface of the clusters. Pure Ni clusters are also known to become encapsulated upon heating, but the reduction of titania is much less extensive compared to that of pure Pt clusters.     

Morphology of Palladium Thin Film Deposited on a Two-Dimensional Bilayer Aluminosilicate

Topics in Catalysis - The morphology of a thin palladium film deposited on bilayer Al0.35Si0.65O2/Ru(0001), previously proposed as a two-dimensional zeolite model, is investigated using a set of...     

Ethanol and Ambrosia Beetles in Douglas Fir Logs Exposed or Protected from Rain

Logs from the base of Douglas fir (Pseudotsuga menziesii) trees cut in October 1993 were randomly assigned to one of three treatment groups: (1) wet logs—cut from the fallen tree and left exposed to rain, (2) dry logs—cut from the fallen tree, placed on blocks, and protected from rain under a plastic tent, and (3) crown logs—left attached to the fallen tree with its branches intact and exposed to rain. The following May, ethanol concentrations were highest in the phloem and sapwood of wet logs (0.24 and 0.35 mol/g fresh wt, respectively). Ethanol concentrations in tissues from dry and crown logs were similar to each other (ranging from 0.002 to 0.03 mol/g fresh wt), but were significantly lower than in wet logs. It appears that rain absorbed by the outer bark of wet logs creates a barrier to gas exchange between living tissues and the atmosphere, which facilitates the development of hypoxic conditions necessary for ethanol synthesis and accumulation. Branches on crown logs exposed to rain help maintain low ethanol concentrations in the log tissues; we discuss several potential mechanisms to explain this response. By early September, the densities of Gnathothrichus spp. gallery entrance holes were high on wet logs (21.5/m²) and low on dry (2.5/m²) and crown logs (5.8/m²), indicating their preference for logs with higher ethanol concentrations. Protecting logs from rain will significantly reduce ethanol concentrations and the density of ambrosia beetle galleries. Leaving branches attached to logs will produce similar results, but its effectiveness may vary depending on the environmental conditions. Host selection by secondary scolytid beetles that use ethanol as a kairomone can be manipulated and possibly managed by controlling the production of ethanol in the host resource.     

Advanced Postirradiation Characterization of Nuclear Fuels Using Pulsed Neutrons

Methods for postirradiation characterization of bulk (cm³) irradiated materials or even spent nuclear fuels are sparse due to their extremely radioactive nature. While several methods exist to characterize smaller volumes (<?1 mm³) of such samples, selecting these volumes from larger samples is challenging. X-ray-based methods are prohibitive due to the strong γ-radiation from the sample flooding the detectors. Neutron-based methods available in the proximity of irradiation reactors allow for thermal neutron radiography or computed tomography using a small reactor source, but one cannot assess isotope distributions or microstructural features such as phases, texture, or strain from diffraction measurements due to flux limitations. We present herein a pathway to provide pulsed neutron characterization of bulk irradiated samples using time-of-flight neutron diffraction for microstructural characterization and energy-resolved neutron imaging for assessment of isotopic densities and distributions. Ultimately, laser-driven pulsed neutron sources may allow deployment of these techniques pool-side at irradiation reactors.

     

Effect of Ambrotose AO<Superscript>®</Superscript> on resting and exercise-induced antioxidant capacity and oxidative stress in healthy adults

Background

The purpose of this investigation was to determine the effects of a dietary supplement (Ambrotose AO^®) on resting and exercise-induced blood antioxidant capacity and oxidative stress in exercise-trained and untrained men and women.

Methods

25 individuals (7 trained and 5 untrained men; 7 trained and 6 untrained women) received Ambrotose AO^® (4 capsules per day = 2 grams per day) or a placebo for 3 weeks in a random order, double blind cross-over design (with a 3 week washout period). Blood samples were collected at rest, and at 0 and 30 minutes following a graded exercise treadmill test (GXT) performed to exhaustion, both before and after each 3 week supplementation period. Samples were analyzed for Trolox Equivalent Antioxidant Capacity (TEAC), Oxygen Radical Absorbance Capacity (ORAC), malondialdehyde (MDA), hydrogen peroxide (H₂O₂), and nitrate/nitrite (NOx). Quality of life was assessed using the SF-12 form and exercise time to exhaustion was recorded. Resting blood samples were analyzed for complete blood count (CBC), metabolic panel, and lipid panel before and after each 3 week supplementation period. Dietary intake during the week before each exercise test was recorded.

Results

No condition effects were noted for SF-12 data, for GXT time to exhaustion, or for any variable within the CBC, metabolic panel, or lipid panel (p > 0.05). Treatment with Ambrotose AO^® resulted in an increase in resting levels of TEAC (p = 0.02) and ORAC (p < 0.0001). No significant change was noted in resting levels of MDA, H₂O₂, or NOx (p > 0.05). Exercise resulted in an acute increase in TEAC, MDA, and H₂O₂ (p < 0.05), all which were higher at 0 minutes post exercise compared to pre exercise (p < 0.05). No condition effects were noted for exercise related data (p > 0.05), with the exception of ORAC (p = 0.0005) which was greater at 30 minutes post exercise for Ambrotose AO^® compared to placebo.

Conclusion

Ambrotose AO^® at a daily dosage of 4 capsules per day increases resting blood antioxidant capacity and may enhance post exercise antioxidant capacity. However, no statistically detected difference is observed in resting or exercise-induced oxidative stress biomarkers, in quality of life, or in GXT time to exhaustion.

     

Effects of drought on the physicochemical,nutrient, and carbon metrics of flows in the Savannah River,Georgia, USA

Hydrological drought has wide-ranging impacts on water quality, nutrient and carbon metrics, and given the uncertainty of climate change and the predicted increased frequency and intensity of drought in the future, investigations into changes induced by drought become increasingly important. This study compared physicochemical parameters (temperature, conductivity, pH and DO), nutrients (TN, NO_X [NO₂ + NO₃], NH₃ and TP) and carbon (TOC and DOC) between hydrological drought conditions (2006–2008) and hydrological normal conditions (2016–2019) at five sites along the lower Savannah River (Georgia, USA). Although we had predicted that water temperatures would increase from drought, we instead found temperature was significantly lower during drought conditions. Levels of pH and DO were significantly higher during drought. Further, TN, TOC and DOC concentrations were significantly lower during drought, but NO_X concentrations were significantly higher during drought. Conductivity varied at the lower river sites, being significantly higher during drought at sites located below the city of Augusta, GA. These complex changes could be attributed to volume reductions coupled with an increase in the percentage of total flow originating from groundwater as well as limnetic reservoir inputs, persistent point source pollution, reduced natural catchment inputs and/or reduced floodplain interactions. The changes that occurred during drought may be disruptive to aquatic life, not only from reduced water quantity but also due to a scarcity of some biologically essential materials and lower food resources, combined with artificially high levels of some other potentially stressful materials.     

Piperidine Alkaloids in Nitrogen Fertilized Pinus ponderosa

We fertilized individual, pole-size ponderosa pine trees at two low-quality sites and pine saplings at a relatively high-quality site, with ammonium nitrate. Six to 12 months later, we measured total %N and 2,6-disubstituted piperidine alkaloids in the foliage. The N additions raised foliar %N above deficiency levels (i.e., from 1.0–1.1% to 1.4–1.6%) at the low-quality sites, but did not elevate foliar %N in saplings at the higher quality site, where it was already (1.9%) well above critical levels. In control trees with foliar N below a threshold of 1.1%, we detected no more than trace levels of alkaloids, indicating that alkaloid production is highly constrained by N deficiency. The N additions increased mean concentrations of the predominant alkaloid, pinidine, at all three sites. Mean total alkaloid concentrations for fertilized trees at the two low-quality sites were 12 and 155 g/g dry wt higher than controls (relative increases of 12× and 4.5×, respectively). For saplings at the high-quality site, the mean total increased by 584 g/g dry wt (1.6×) with the N additions. Allocation of foliar N to alkaloids was highest in fertilized saplings (0.81%) compared to control saplings (0.53%). These findings demonstrate that foliar alkaloid concentrations can be increased by nitrogen fertilization of forest trees growing on both low- and high-quality sites. Fertilizing for the purpose of inhibiting potential herbivores may be more successful at higher quality sites where alkaloid levels are enhanced relative to food quality (foliar %N).     

X-ray diffraction investigation of bimetallic diffusion zones in the Cu-Pd system

A nondestructive X-ray diffraction technique was used to investigate the diffusion of 8β thick deposits of Pd into [100] oriented single crystals of Cu. The concentration profiles produced by isothermal diffusion at 900°C were determined by mathematical analyses of two diffracted intensity bands. The Boltzmann-Matano analysis was used to determine concentration dependent diffusion coefficients which were found to compare favorably with previously reported values. Also, X-ray rocking curves were made on selected compositions to determine the degree of diffusion-generated subgrain misorientation increase in the diffusion zones. These rocking curves were Gaussian in shape and indicated that the distribution of subgrain misorientations was Gaussian. The widths of the Gaussian misorientation functions were found to be directly related to the lattice parameter gradient existing in the specimen after diffusion. The results of this investigation are compared with those obtained from a previous examination of nearly identically prepared Cu-Ni specimens.