Glyoxal, the simplest and most abundant alpha-dicarbonyl compound in the atmosphere, is scavenged by clouds and aerosol, where it reacts with nucleophiles to form low-volatility products. Here we examine the reactions of glyoxal with five amino acids common in clouds. When glyoxal and glycine, serine, aspartic acid or ornithine are present at concentrations as low as 30/microM in evaporating aqueous droplets or bulk solutions, 1,3-disubstituted imidazoles are formed in irreversible second-order reactions detected by nuclear magnetic resonance (NMR), aerosol mass spectrometry (AMS) and electrospray ionization mass spectrometry (ESI-MS). In contrast, glyoxal reacts with arginine preferentially at side chain amino groups, forming nonaromatic five-membered rings. All reactions were accompanied by browning. The uptake of 45 ppb glyoxal by solid-phase glycine aerosol at 50% RH was also studied and found to cause particle growth and the production of imidazole measured by scanning mobility particle sizing and AMS, respectively, with a glyoxal uptake coefficient alpha = 0.0004. Comparison of reaction kinetics in bulk and in drying droplets shows that conversion of glyoxal dihydrate to monohydrate accelerates the reaction by over 3 orders of magnitude, allowing these reactions to occur at atmospheric conditions.
Recruitment of neutrophils to the airways, and their pathological conditioning therein, drive tissue damage and coincide with the loss of lung function in patients with cystic fibrosis (CF). So far, these key processes have not been adequately recapitulated in models, hampering drug development. Here, we hypothesized that the migration of naïve blood neutrophils into CF airway fluid in vitro would induce similar functional adaptation to that observed in vivo, and provide a model to identify new therapies. We used multiple platforms (flow cytometry, bacteria-killing, and metabolic assays) to characterize functional properties of blood neutrophils recruited in a transepithelial migration model using airway milieu from CF subjects as an apical chemoattractant. Similarly to neutrophils recruited to CF airways in vivo, neutrophils migrated into CF airway milieu in vitro display depressed phagocytic receptor expression and bacterial killing, but enhanced granule release, immunoregulatory function (arginase-1 activation), and metabolic activities, including high Glut1 expression, glycolysis, and oxidant production. We also identify enhanced pinocytic activity as a novel feature of these cells. In vitro treatment with the leukotriene pathway inhibitor acebilustat reduces the number of transmigrating neutrophils, while the metabolic modulator metformin decreases metabolism and oxidant production, but fails to restore bacterial killing. Interestingly, we describe similar pathological conditioning of neutrophils in other inflammatory airway diseases. We successfully tested the hypothesis that recruitment of neutrophils into airway milieu from patients with CF in vitro induces similar pathological conditioning to that observed in vivo, opening new avenues for targeted therapeutic intervention.
This article analyzes the financial ties between congressional candidates and individual donors residing outside those candidates' districts. Congressional campaigns today rely more heavily on nonresidents than in the past, with contests in the typical district drawing more than two-thirds of individual donations from nonresidents. Empirical results reveal that nonresident contributions are primarily partisan and strategic in nature, rather than access-oriented or expressive/identity-based. Funds are efficiently redistributed from a small number of highly educated, wealthy congressional districts to competitive districts anywhere in the country. Big donors direct funds where they can make a difference for party control of seats, even if those investments are hundreds, or even thousands, of miles away.
This article examines the geographic origins of individual campaign contributions to the Republican and Democratic parties and their candidates from 1992 to 2004. Results demonstrate that contributions are affected by how potential givers are situated in space. There is a geographic pattern to giving independent of wealth, age, occupation, and other individual characteristics that predict donations. Campaign contributors are not only people with resources and incentives to participate, but also part of networks in which social influence can be brought to bear in the solicitation of contributions. The article also shows that the Republican and Democratic donor bases are much more similar geographically than their bases of electoral support. campaigns need financial resources. This article sets campaign contributions in geographic context to answer two important questions about campaign contributions.First, where do parties and major party candidates raise their funds? Much ink has been spilled recently about the rivalry between "red" and "blue" electorates and the extent to which the parties have either distinctive or intersecting bases of mass support. Contributing, a demanding form of political participation, is not uniformly distributed throughout the population (Brady, Schlozman, and Verba 1999;Verba et al. 1993). While giving is undeniably associated with wealth, many people who can afford to give do not do so, while others give beyond their means. If the major parties have dissimilar geographic bases of electoral support, do they also have different bases of financial support? In an era when the two major parties appear to be well matched in their capacity to raise funds, determining where the gold is most profitably mined contributes to practical and scientific knowledge about politics.Second, does geographic context have an independent effect on campaign contributions? The geographic distribution of campaign contributions could be merely an artifact of the spatial distribution of individuals with the resources and inclination to give. However, there is good reason to expect otherwise,
This article argues that scholars need to consider the structure of House representation to better understand distributive politics. Because House districts (unlike states) are not administrative units in the federal system, House members cannot effectively claim credit for most grant-in-aid funds. Instead, their best credit-claiming opportunities lie in earmarked projects, a small fraction of federal grant dollars. As a consequence, I expect to find: (1) political factors have a much greater effect on the distribution of earmarked projects than on federal funds generally; and (2) project grants are a better support-building tool for coalition leaders than allocations to states. I test this argument with a study of the 1998 reauthorization of surface transportation programs and find strong support for both hypotheses.
The Senate's equal representation of states shapes coalition building in distributive politics. The great variation in state population means that some states have far greater need for federal funds than others, but all senators have equal voting weight. As a result, even though all senators' votes are of equal value to the coalition builder, they are not of equal “price.” Coalition builders can include benefits for small states at considerably less expense to program budgets than comparable benefits for more populous states. Building on formal models of coalition building, two hypotheses are developed and tested. First, coalition builders will seek out less costly members to build supportive coalitions efficiently. Second, the final outcomes of distributive policy will more closely reflect the preferences of small-state senators than large-state senators. The hypotheses are tested by examining the 1991 and 1997–98 reauthorizations of federal surface transportation programs. The findings support both hypotheses.
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