We measured the rate of generation of reactive oxygen species (ROS) [hydroxyl radicals (OH) and hydrogen peroxide (HO)] catalyzed by ambient particulate matter (PM) in the dithiothreitol (DTT) assay. To understand the mechanism of ROS generation, we tested several redox-active substances, such as 9,10-phenanthrenequinone (PQ), 5-hydroxy-1,4-naphthoquinone (5H-1,4NQ), 1,2-naphthoquinone (1,2-NQ), 1,4-naphthoquinone (1,4-NQ), copper(II), manganese(II), and iron (II and III). Both pure compounds and their mixtures show different patterns in DTT oxidation versus ROS generation. The quinones, known to oxidize DTT in the efficiency order of PQ > 5H-1,4NQ > 1,2-NQ > 1,4-NQ, show a different efficiency order (5H-1,4NQ > 1,2-NQ ≈ PQ > 1,4-NQ) in the ROS generation. Cu(II), a dominant metal in DTT oxidation, contributes almost negligibly to the ROS generation. Fe is mostly inactive in DTT oxidation, but shows synergistic effect in OH formation in the presence of other quinones (mixture/sum> 1.5). Ten ambient PM samples collected from an urban site were analyzed, and although DTT oxidation was significantly correlated with HO generation (Pearson's r = 0.91), no correlation was observed between DTT oxidation and OH formation. Our results show that measuring both DTT consumption and ROS generation in the DTT assay is important to incorporate the synergistic contribution from different aerosol components and to provide a more inclusive picture of the ROS activity of ambient PM.

No abstract

We assessed the interactions among the particulate matter (PM) components in generating the reactive oxygen species (ROS) based on a dithiothreitol (DTT) assay. We started with the standard solutions of known redox-active substances, i.e., quinones (9,10-phenanthraquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, and 5-hydroxy-1,4-naphthoquinone) and metals [Fe (II), Mn (II), and Cu (II)]. Both DTT consumption and hydroxyl radical (·OH) generation were measured in the DTT assay. The interactions of Fe were additive with quinones in DTT consumption but strongly synergistic in ·OH generation. Cu showed antagonistic interactions with quinones in both DTT consumption and ·OH generation. Mn interacted synergistically with quinones in DTT oxidation but antagonistically in ·OH generation. The nature of the interactions of these metals (Fe, Mn, and Cu) with ambient humic-like substances (HULIS) resembled that with quinones, although the intensity of interactions were weaker in DTT consumption than ·OH generation. Finally, we demonstrated that the DTT consumption capability of ambient PM can be well explained by HULIS, three transition metals (Fe, Mn, and Cu), and their interactions, but ·OH generation involves a contribution (∼50%) from additional compounds (aliphatic species or metals other than Fe, Mn, and Cu) present in the hydrophilic PM fraction. The study highlights the need to account for the interactions between organic compounds and metals, while apportioning the relative contributions of chemical components in the PM oxidative potential.

Memory devices with high speed and high density are highly desired to address the 'memory wall' issue. Here we demonstrated a highly scalable, three-dimensional stackable ferroelectric diode, with its rectifying polarity modulated by the polarization reversal of Hf 0.5 Zr 0.5 O 2 films. By visualizing the hafnium/zirconium lattice order and oxygen lattice order with atomicresolution spherical aberration-corrected STEM, we revealed the correlation between the spontaneous polarization of Hf 0.5 Zr 0.5 O 2 film and the displacement of oxygen atom, thus unambiguously identified the non-centrosymmetric Pca2 1 orthorhombic phase in Hf 0.5 Zr 0.5 O 2 film. We further implemented this ferroelectric diode in an 8 layers 3D array. Operation speed as high as 20 ns and robust endurance of more than 10 9 were demonstrated. The builtin nonlinearity of more than 100 guarantees its self-selective property that eliminates the need for external selectors to suppress the leakage current in large array. This work opens up new opportunities for future memory hierarchy evolution.

No abstract

We investigated the complexation state of atmospheric iron and copper and its impact on the oxidative potential (OP) of ambient PM2.5 (PM, particulate matter). A novel fractionation scheme was developed to segregate three different fractions of Fe and Cu present in ambient PM2.5: (i) complexed with hydrophobic organic compounds, (ii) complexed with hydrophilic organic compounds, and (iii) free or inorganic metal fraction. A solid phase extraction (C-18) column was used to separate these fractions. The fractionation scheme applied to the ambient PM2.5 samples collected from an urban site showed that up to 70–90% of water-soluble Fe and Cu were complexed with the organic compounds. The capability of the complexes of Fe­(II) and Cu­(II) with Suwanee river fulvic acid (SRFA), a proxy for the atmospheric organic compounds, to generate reactive oxygen species (ROS) (·OH and H2O2) in a surrogate lung fluid (SLF) was measured. The complex of Fe–SRFA showed a strong synergistic effect in the generation of ·OH in SLF, while that of Cu–SRFA showed an additive effect. Overall, our results indicate that organic complexation of the metals in ambient PM could significantly alter their OP and needs to be considered while assessing their health impacts.

We report details on the synthesis and electrochemistry of quinone-type methanofullerene derivatives in which, depending upon the substitution pattern on the cyclohexanedienone moiety, the reduction potential can be tuned, leading to novel fullerene derivatives exhibiting better acceptor properties than C 60 . We also present the lowest energy conformers of these spiroannulated methanofullerenes. As expected, the anthrone derivative is not coplanar and is not perpendicular to the ball's surface.

Cell motion within a liquid suspension inside a piezoelectrically actuated, cylindrical inkjet printhead was studied using high speed imaging and a low depth of field setup. For each ejected droplet, a cell within the inkjet nozzle was observed to exhibit one of three possible behaviors which are termed: cell travel, cell ejection and cell reflection. Cell reflection is an undesirable phenomenon which may adversely affect an inkjet's capability in dispensing cells and a possible reason why it was previously reported that the rate of cells dispensed did not follow the expected Poisson distribution. Through the study of the cells motions, it was hypothesized that the rheological properties of the media in the cell suspension play an important role in influencing the cell behaviors exhibited. This was experimentally studied with the tracking of cells within the inkjet nozzle in a 10% w/v Ficoll PM400 cell suspension. The effect of cell reflection was eliminated using the higher density and viscosity Ficoll PM400 suspension. The presented work is the first in-depth study of the cell behaviors occurring within a piezoelectric inkjet nozzle during the printing process. The understanding of the hydrodynamics during a droplet ejection and its effect on the suspended cells are imperative towards achieving reliable cell dispensing for biofabrication applications.