Kaolinite-catalyzed air oxidation of hydrazine: Consideration of several compositional, structural and energetic factors in surface activation

Clay minerals have been shown to have numerous, curious, energetic properties by virtue of ultra-violet light release which can be triggered by gentle environmental changes such as wetting and dewetting by a variety of liquids, unique among them water and hydrazine. Since both water and hydrazine play multiple key roles in the air-oxidation of hydrazine on kaolinite surfaces, this reaction would seem to have prime potential for studying interrelationships of energy storage, release and chemical reactivity of clay surfaces, capacities basic to either the Bernal or Cairns-Smith roles of minerals in the origin of life. Establishment of the capacity for stored electronic energy to significantly alter surface chemistry is important, regardless of the reaction chosen to demonstrate it. Hydrazine air oxidation is overawingly complex, given the possibilities for step-wise control and monitoring of parameters. In the light of recently extended characterization of the kaolinite and model sheet catalysts we used to study hydrazine oxidation and gamma-irradiated silica, previous studies of hydrazine air-oxidation on aluminosilicate surfaces have been reevaluated. Our former conclusion remains intact that, whereas trace structural and surface contaminants do play some role in the catalysis of oxidation, they are not the only, nor even the dominant, catalytic centers. Initial intermediates in the oxidation can now be proposed which are consistent with production via O(-)-centers as well as ferric iron centers. The greater than square dependence of the initial reaction rate on the weight of the clay is discussed in the light of these various mechanistic possibilities

Making Rasch decisions: The use of Rasch analysis in the construction of preference based health related quality of life instruments

Objective: To set out the methodological process for using Rasch analysis alongside traditional psychometric methods in the development of a health state classification that is amenable to valuation. Methods: The overactive bladder questionnaire is used to illustrate a four step process for deriving a reduced health state classification from an existing nonpreference based health related quality of life instrument. Step I excludes items that do not meet the initial validation process and step II uses criteria based on Rasch analysis and psychometric testing to select the final items for the health state classification. In step III, item levels are examined and Rasch analysis is used to explore the possibility of reducing the number of item levels. Step IV repeats steps I to III on alternative data sets in order to validate the selection of items for the health state classification. Conclusions: The techniques described enable the construction of a health state classification amenable for valuation exercises that will allow the derivation of preference weights. Thus, the health related quality of life of patients with conditions, like overactive bladder, can be valued and quality adjustment weights such as quality adjusted life years derived

Gonadal hormones, but not sex, affect the acquisition and maintenance of a Go/No-Go odor discrimination task in mice

In mice, olfaction is crucial for identifying social odors (pheromones) that signal the presence of suitable mates. We used a custom-built olfactometer and a thirst-motivated olfactory discrimination Go/No-Go (GNG) task to ask whether discrimination of volatile odors is sexually dimorphic and modulated in mice by adult sex hormones. Males and females gonadectomized prior to training failed to learn even the initial phase of the task, which involved nose poking at a port in one location obtaining water at an adjacent port. Gonadally intact males and females readily learned to seek water when male urine (S+) was present but not when female urine (S−) was present; they also learned the task when non-social odorants (amyl acetate, S+; peppermint, S−) were used. When mice were gonadectomized after training the ability of both sexes to discriminate urinary as well as non-social odors was reduced; however, after receiving testosterone propionate (castrated males) or estradiol benzoate (ovariectomized females), task performance was restored to pre-gonadectomy levels. There were no overall sex differences in performance across gonadal conditions in tests with either set of odors; however, ovariectomized females performed more poorly than castrated males in tests with non-social odors. Our results show that circulating sex hormones enable mice of both sexes to learn a GNG task and that gonadectomy reduces, while hormone replacement restores, their ability to discriminate between odors irrespective of the saliency of the odors used. Thus, gonadal hormones were essential for both learning and maintenance of task performance across sex and odor type.We thank David Giese for help in programming the apparatus used in GNG testing and Alberto Cruz-Martin for comments on an early version of the manuscript. This work was supported by NIDCD grant DC008962 to JAC. (DC008962 - NIDCD grant)Accepted manuscrip

Making Rasch decisions: the use of Rasch analysis in the construction of preference based health related quality of life instruments

Objective: To set out the methodological process for using Rasch analysis alongside traditional psychometric methods in the development of a health state classification that is amenable to valuation. Methods: The overactive bladder questionnaire is used to illustrate a four step process for deriving a reduced health state classification from an existing nonpreference based health related quality of life instrument. Step I excludes items that do not meet the initial validation process and step II uses criteria based on Rasch analysis and psychometric testing to select the final items for the health state classification. In step III, item levels are examined and Rasch analysis is used to explore the possibility of reducing the number of item levels. Step IV repeats steps I to III on alternative data sets in order to validate the selection of items for the health state classification. Conclusions: The techniques described enable the construction of a health state classification amenable for valuation exercises that will allow the derivation of preference weights. Thus, the health related quality of life of patients with conditions, like overactive bladder, can be valued and quality adjustment weights such as quality adjusted life years derived.Rasch analysis; health related quality of life; condition specific measure; preference-based measures; overactive bladder syndrome

Making Rasch decisions: The use of Rasch analysis in the construction of preference based health related quality of life instruments

Objective: To set out the methodological process for using Rasch analysis alongside traditional psychometric methods in the development of a health state classification that is amenable to valuation. Methods: The overactive bladder questionnaire is used to illustrate a four step process for deriving a reduced health state classification from an existing nonpreference based health related quality of life instrument. Step I excludes items that do not meet the initial validation process and step II uses criteria based on Rasch analysis and psychometric testing to select the final items for the health state classification. In step III, item levels are examined and Rasch analysis is used to explore the possibility of reducing the number of item levels. Step IV repeats steps I to III on alternative data sets in order to validate the selection of items for the health state classification. Conclusions: The techniques described enable the construction of a health state classification amenable for valuation exercises that will allow the derivation of preference weights. Thus, the health related quality of life of patients with conditions, like overactive bladder, can be valued and quality adjustment weights such as quality adjusted life years derived

Pushing on a string? An argument for civil society-driven community policing as alternative to ministry-centric approach in conflict-affected states

Most international support for community policing focuses primarily if not exclusively on capacity building of the government, namely Ministries of Interior and police forces. For structural reasons, these organizations -in and of themselves- are often not the most appropriate partners to launch or sustain community-oriented policing initiatives, especially in the early phases of police reform. This paper presents an alternative to the ministry-centric approach in the form of civil society-driven programming for police reform. Using the case of police reform in Afghanistan in the late 2000s, we argue that a focus on community engagement, accountability, and responsiveness to the needs of the population can lead to improved human security even in post-conflict countries. Although a grassroots approach may seem daunting international actors more familiar with strategic advising at the ministerial level, we find that it provides an opportunity for more sustainable and effective engagement than ministry-centric efforts alone. Our experience from the Afghanistan case also shows, however, that a civil society approach is not a standalone - it needs to be complemented by ministerial initiatives as government has the central role in directing police reform. Adding a civil society component can make the official efforts more likely to succeed

Evolution of Protein Expression: New Genes for a New Diet

SummaryA new study identifies gene duplication of a salivary enzyme as a recent adaptation to changes in diet among human populations, highlighting the diverse ways that gene regulation can evolve