RESPONSE OF SOME SCOLYTIDS AND THEIR PREDATORS TO ETHANOL AND 4-ALLYLANISOLE IN PINE FORESTS OF CENTRAL OREGON

Lindgren multiple funnel traps were set up in pine forests of central Oregon to determine the response of scolytid bark beetles to ethanol and 4-allylanisole (4AA). Traps were baited with two release rates of ethanol (4.5 or 41.4 mg/hr) and three release rates of 4AA (0, 0.6, or 4.3 mg/hr) in a 2 × 3 factorial design. All traps also released a 1:1 mixture of - and -pinene at 11.4 mg/hr. Of 13,396 scolytids caught, Dendroctonus valens made up 60%, Hylurgops spp. 18.5%, Ips spp. 16%, Hylastes spp. 1.8%, Ganthotrichus retusus 0.9%, and bark beetle predators another 2.8%. Increasing the release rate of ethanol in the absence of 4AA increased the number of most scolytid species caught by 1.5–3.7 times, confirming its role as an attractant. Ips latidens, Temnochila chlorodia, and clerid predators were exceptions and did not show a response to higher ethanol release rates. Release of 4AA at the lowest rate inhibited attraction of most scolytids, with a significant reduction in G. retusus, Hylastes macer, and Hylurgops porosus when compared to traps without 4AA. A high release rate of 4AA further inhibited responses for most beetles compared to low 4AA. Seven species were significantly deterred by high 4AA, including the latter three, and Hylastes longicollis, Hylastes nigrinus, Hylurgops reticulatus, and Ips latidens. Exceptions include Hylurgops subcostulatus, which was significantly attracted to both low and high 4AA, and I. pini, which was attracted to low and high 4AA in combination with low ethanol, but unaffected by either release of 4AA with high ethanol. Dendroctonus valens was significantly attracted to low 4AA and unaffected by high 4AA. Predators appeared to be less inhibited by 4AA than most bark beetles. Although 4AA can deter the attraction of some secondary bark beetles to ethanol in combination with - and -pinene, this inhibition could be weakened for certain species by increasing ethanol release rates. 4-Allylanisole may have some utility for managing the behavior of secondary bark beetles sensitive to this compound.     

The new chemical biology of nitrite reactions with hemoglobin: R-state catalysis, oxidative denitrosylation, and nitrite reductase/anhydrase

Because of their critical biological roles, hemoglobin and myoglobin are among the most extensively studied proteins in human history, while nitrite tops the list of most-studied small molecules. And although the reactions between them have been examined for more than 140 years, a series of unusual and critical allosterically modulated reactions have only recently been characterized. In this Account, we review three novel metal- and nitrite-catalyzed reaction pathways in the context of historical studies of nitrite and hemoglobin chemistry and attempt to place them in the biological framework of hypoxic signaling. Haldane first described the reaction between nitrite and deoxymyoglobin, forming iron-nitrosylated myoglobin, in his analysis of the meat-curing process more than a century ago. The reaction of nitrous acid with deoxyhemoglobin to form nitric oxide (NO) and methemoglobin was more fully characterized by Brooks in 1937, while the mechanism and unusual behavior of this reaction were further detailed by Doyle and colleagues in 1981. During the past decade, multiple physiological studies have surprisingly revealed that nitrite represents a biological reservoir of NO that can regulate hypoxic vasodilation, cellular respiration, and signaling. Importantly, chemical analysis of this new biology suggests a vital role for deoxyhemoglobin- and deoxymyoglobin-dependent nitrite reduction in these processes. The use of UV-vis deconvolution and electron paramagnetic resonance (EPR) spectroscopy, in addition to refined gas-phase chemiluminescent NO detection, has led to the discovery of three novel and unexpected chemistries between nitrite and deoxyhemoglobin that may contribute to and facilitate hypoxic NO generation and signaling. First, R-state, or allosteric, autocatalysis of nitrite reduction increases the rate of NO generation by deoxyhemoglobin and results in maximal NO production at approximately 50% hemoglobin oxygen saturation, which is physiologically associated with greatest NO-dependent vasodilation. Second, oxidative denitrosylation of the iron-nitrosyl product formed in the deoxyhemoglobin-nitrite reaction allows for NO formation and release in a partially oxygenated environment. Finally, the deoxyhemoglobin-nitrite reaction participates in a nitrite reductase/anhydrase redox cycle that catalyzes the anaerobic conversion of two molecules of nitrite into dinitrogen trioxide (N(2)O(3)). N(2)O(3) may then nitrosate proteins, diffuse across hydrophobic erythrocyte membrane channels such as aquaphorin or Rh, or reconstitute NO via homolysis to NO and NO(2)(*). Importantly, the nitrite reductase/anhydrase redox pathway also represents a novel mechanism of both anaerobic and metal-catalyzed N(2)O(3) formation and S-nitrosation and may thus play a vital role in NO-dependent signaling in a hypoxic and heme-rich environment. We consider how these reactions may contribute to physiological and pathological hypoxic signaling.     

Characterization of the free energy spectrum of peptostreptococcal protein L

BACKGROUND: Native state hydrogen/deuterium exchange studies on cytochrome c and RNase H revealed the presence of excited states with partially formed native structure. We set out to determine whether such excited states are populated for a very small and simple protein, the IgG-binding domain of peptostreptococcal protein L. RESULTS: Hydrogen/deuterium exchange data on protein L in 0-1.2 M guanidine fit well to a simple model in which the only contributions to exchange are denaturant-independent local fluctuations and global unfolding. A substantial discrepancy emerged between unfolding free energy estimates from hydrogen/deuterium exchange and linear extrapolation of earlier guanidine denaturation experiments. A better determined estimate of the free energy of unfolding obtained by global analysis of a series of thermal denaturation experiments in the presence of 0-3 M guanidine was in good agreement with the estimate from hydrogen/deuterium exchange. CONCLUSIONS: For protein L under native conditions, there do not appear to be partially folded states with free energies intermediate between that of the folded and unfolded states. The linear extrapolation method significantly underestimates the free energy of folding of protein L due to deviations from linearity in the dependence of the free energy on the denaturant concentration.     

Heterogeneity Within and Across Households in Hurricane Evacuation Response

A survey of Houston-area households reveals responses to Hurricane Ike in 2008 were as diverse as the households themselves. Review of evacuation literature shows this remains a fundamental problem. In our analysis no clear correlations between household attributes and evacuation motivators emerge unless the respondents are organized into subpopulations based on household attributes and the stated concerns of survey respondents. These subpopulations overlap so that most households fall within multiple classifications, evidence that heterogeneity across households is also present within them. To address heterogeneity within households, an information content metric (information entropy) is considered a proxy for issue saliency. Focusing on the most salient responses to survey questions makes it possible to isolate some of the factors important in the decision to evacuate and the characteristics of the households for which those factors are most important. Regression analysis of the most salient issues of the most concerned respondents informs the creation of behavioral rules for an agent-based model populated with the survey data. The relative strengths of the risk-averting behavior rules are tuned through Monte Carlo simulations using the actual evacuation time of each household as the fitness metric.