Chemistry, Department of

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Water Oxidation by a Cytochrome P450: Mechanism and Function of the Reaction

Peer reviewed: 
Yes, item is peer reviewed.
Date created: 
2013
Abstract: 

P450cam (CYP101A1) is a bacterial monooxygenase that is known to catalyze the oxidation of camphor, the first committed step in camphor degradation, with simultaneous reduction of oxygen (O2). We report that P450cam catalysis is controlled by oxygen levels: at high O2 concentration, P450cam catalyzes the known oxidation reaction, whereas at low O2 concentration the enzyme catalyzes the reduction of camphor to borneol. We confirmed, using 17O and 2H NMR, that the hydrogen atom added to camphor comes from water, which is oxidized to hydrogen peroxide (H2O2). This is the first time a cytochrome P450 has been observed to catalyze oxidation of water to H2O2, a difficult reaction to catalyze due to its high barrier. The reduction of camphor and simultaneous oxidation of water are likely catalyzed by the iron-oxo intermediate of P450cam, and we present a plausible mechanism that accounts for the 1:1 borneol:H2O2 stoichiometry we observed. This reaction has an adaptive value to bacteria that express this camphor catabolism pathway, which requires O2, for two reasons: 1) the borneol and H2O2 mixture generated is toxic to other bacteria and 2) borneol down-regulates the expression of P450cam and its electron transfer partners. Since the reaction described here only occurs under low O2 conditions, the down-regulation only occurs when O2 is scarce.

Document type: 
Article
File(s): 

Synthesis of Ag Nanostructures by Photochemical Reduction Using Citrate-Capped Pt Seeds

Peer reviewed: 
Yes, item is peer reviewed.
Date created: 
2011
Abstract: 

A simple synthesis of Ag nanostructures such as nanorods and nanowires has been demonstrated with citrate-capped Pt seeds. UV-visible spectra and photographs of the synthesized solutions at different UV exposure times showed that the citrate-capped Pt seed played a crucial role in the growth of Ag nanostructures. After UV exposure of the colloidal solution for 60 min, the average diameter, length, and aspect ratio of the Ag nanostructures were about 95 nm, 2.1 nm, and 22, respectively. The photochemical reduction is hypothesized to result from photoelectron transfer from adsorbed citrate to Pt nanoparticle seed allowing Ag ions to form Ag nanostructures. Based on X-ray diffraction spectra and transmission electron microscope images, the synthesized Ag nanostructures were a face-centered cubic single crystal with good purity. These results suggest that the photochemical reduction method can provide Ag nanostructures in the presence of citrate-capped Pt seeds at room temperature for anisotropic Ag products.

Document type: 
Article

New Insights into Honey Bee (Apis mellifera) Pheromone Communication. Is the Queen Mandibular Pheromone Alone in Colony Regulation?

Peer reviewed: 
Yes, item is peer reviewed.
Date created: 
2010
Abstract: 

Background: In social insects, the queen is essential to the functioning and homeostasis of the colony. This influencehas been demonstrated to be mediated through pheromone communication. However, the only social insect forwhich any queen pheromone has been identified is the honey bee (Apis mellifera) with its well-known queenmandibular pheromone (QMP). Although pleiotropic effects on colony regulation are accredited to the QMP, thispheromone does not trigger the full behavioral and physiological response observed in the presence of the queen,suggesting the presence of additional compounds. We tested the hypothesis of a pheromone redundancy in honeybee queens by comparing the influence of queens with and without mandibular glands on worker behavior andphysiology.Results: Demandibulated queens had no detectable (E)-9-oxodec-2-enoic acid (9-ODA), the major compound in QMP,yet they controlled worker behavior (cell construction and queen retinue) and physiology (ovary inhibition) asefficiently as intact queens.Conclusions: We demonstrated that the queen uses other pheromones as powerful as QMP to control the colony. Itfollows that queens appear to have multiple active compounds with similar functions in the colony (pheromoneredundancy). Our findings support two hypotheses in the biology of social insects: (1) that multiple semiochemicalswith synonymous meaning exist in the honey bee, (2) that this extensive semiochemical vocabulary exists because itconfers an evolutionary advantage to the colony.

Document type: 
Article