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Many COVID-19 survivors have post-COVID-19 conditions, and females are at a higher risk. We sought to determine (1) how protein levels change from acute to post-COVID-19 conditions, (2) whether females have a plasma protein signature different from that of males, and (3) which biological pathways are associated with COVID-19 when compared to restrictive lung disease. We measured protein levels in 74 patients on the day of admission and at 3 and 6 months after diagnosis. We determined protein concentrations by multiple reaction monitoring (MRM) using a panel of 269 heavy-labeled peptides. The predicted forced vital capacity (FVC) and diffusing capacity of the lungs for carbon monoxide (DLCO) were measured by routine pulmonary function testing. Proteins associated with six key lipid-related pathways increased from admission to 3 and 6 months; conversely, proteins related to innate immune responses and vasoconstriction-related proteins decreased. Multiple biological functions were regulated differentially between females and males. Concentrations of eight proteins were associated with FVC, %, and they together had c -statistics of 0.751 (CI:0.732-0.779); similarly, concentrations of five proteins had c -statistics of 0.707 (CI:0.676-0.737) for DLCO, %. Lipid biology may drive evolution from acute to post-COVID-19 conditions, while activation of innate immunity and vascular regulation pathways decreased over that period. (ProteomeXchange identifiers: PXD041762, PXD029437).

The fabrication of controlled, self-organized, highly ordered tungsten and aluminum nanorods was accomplished via the aluminum lattice template-assisted glancing angle sputtering technique. The typical growth mechanism of traditional glancing angle deposition technique was biased by self-organized aluminum lattice seeds resulting in superior quality nanorods in terms of size control, distribution, and long range order. The morphology, size, and distribution of the nanorods were highly controlled by the characteristics of the template seeds indicating the ability to obtain metallic nanorods with tunable distributions and morphologies that can be grown to suit a particular application. Water wettability of hexagonally arranged tungsten and aluminum nanorods was studied after modifying their surface with 5 nm of Teflon AF 2400, as an example, to exhibit the significance of such a controlled growth of metallic nanorods. This facile and scalable approach to generate nano seeds to guide GLAD, with nano seeds fabricated by anodic oxidization of aluminum followed by chemical etching, for the growth of highly ordered nanorods could have significant impact in a wide range of applications such as anti-icing coating, sensors, super capacitors, and solar cells.

The nature of water interaction with tungsten nanorods (WNRs) fabricated by the glancing-angle deposition technique (GLAD)-using RF magnetron sputtering under various Ar pressures and substrate tilting angles and then subsequent coating with Teflon-has been studied and reported. Such nanostructured surfaces have shown strong water repellency properties with apparent water contact angles (AWCA) of as high as 160°, which were found to depend strongly upon the fabrication conditions. Variations in Ar pressure and the substrate tilting angle resulted in the generation of WNRs with different surface roughness and porosity properties. A theoretical model has been proposed to predict the observed high AWCAs measured at the nanostructure interfaces. The unique pyramidal tip geometry of WNRs generated at low Ar pressure with a high oblique angle reduced the solid fraction at the water interface, explaining the high AWCA measured on such surfaces. It was also found that the top geometrical morphologies controlling the total solid fraction of the WNRs are dependent upon and controlled by both the Ar pressure and substrate tilting angle. The water repellency of the tungsten nanorods with contact angles as high as 160° suggests that these coatings have enormous potential for robust superhydrophobic and anti-icing applications in harsh environments., (© 2011 American Chemical Society)

The bacterial flavoprotein monooxygenase carries out an oxygen insertion reaction on cyclohexanone, with ring expansion to form the seven-membered cyclic product epsilon-caprolactone, a transformation quite distinct from the phenol leads to catechol transformation carried out by the bacterial flavoprotein aromatic hydroxylases. Cyclohexanone oxygenase catalysis involves the four-electron of O2 at the expense of a two-electron oxidation of NADPH, concomitant with a two-electron oxidation of cyclohexanone to epsilon-caprolactone. NADPH oxidase activity is fully coupled with oxygen transfer to substrate. Steady-state kinetic assays demonstrate a ter-ter mechanism for this enzyme. Pre-steady-state kinetic assays demonstrate the participation of a 4a-hydroperoxyflavin intermediate during catalysis. In addition to its ketolactonizing activity, cyclohexanone oxygenase carries out S-oxygenation of thiane to thiane 1-oxide, a reaction which represents a nucleophilic displacement by the sulfur upon the terminal oxygen of the hydroperoxide. This is in contrast to cyclohexanone oxygenations where the flavin hydroperoxide acts as a nucleophile. In addition, a stable apoenzyme form is accessible and can be reconstituted with various FAD analogues with up to 100% recovery of enzyme activity. The accumulated results presented here support a Baeyer-Villiger rearrangement mechanism for the enzymatic oxygenation of cyclohexanone.

Three bacterial flavoprotein monooxygenases, p-hydroxybenzoate hydroxylase, orcinol hydroxylase, and salicylate hydroxylase, have been examined for steady-state kinetic isotope effects with (4R)-[4-2H]NAD(P)H and (4R)-[4-3H]NAD(P)H. The observed isotope selections are for deuterium, DV = 1.8-3.5 and D(V/K) = 1.7-5.1, and for tritium, T(V/K) = 5-19. For both orcinol hydroxylase and p-hydroxybenzoate hydroxylase, reduction of enzyme-bound FAD by (4R)-[4-2H]NAD(P)H in pre-steady-state assays reveals intrinsic deuterium isotope effects of 10 +/- 2 on this redox step. These values are at the upper end of substrate deuterium effects seen in enzymatic reactions. Suppression of approximately 83% of the intrinsic isotope effects in the overall reaction rate (e.g., kH/kD = 10 down to DV = 2.5) corroborates earlier kinetic data on p-hydroxybenzoate hydroxylase [Husain, M., & Massey. V. (1979) J. Biol. Chem. 254, 6657] and suggests that these bacterial phenolic monooxygenases balance out internal transition states such that no single barrier is fully rate limiting.