Ion-molecule reactions reveal facile radical migration in peptides

Ion-molecule reactions between molecular oxygen and peptide radicals in the gas phase demonstrate that radical migration occurs easily within large biomolecules without addition of collisional activation energy.

Unusual cross-ring S(N)2 reactions of M-H (-) ions of methoxyacetanilides

Deprotonated o, m-, and p-methoxyacetanilide show pronounced peaks in their collision-induced tandem mass spectra (MS/MS) produced by losses of the elements of C2H6. It is proposed that this reaction is a 'cross-ring' internal S(N)2 reaction involving an incipient methyl anion. For example, p-CH3O-C6H4-N--CO-CH3--> [(p.CH3O-C6H4-N=C=O)CH3-]--> O---C6H4-N=C=O+C2H6.

Anionic migration reactions in aromatic systems effected by collisional activation : Deprotonated anilides containing methoxycarbonyl substituents

Long-range cross-ring reactions are of minor importance in the collision-induced mass spectra (MS/MS) of [M - H]- ions of CH2OCO-C6H4-NHCOR systems: e.g. the loss of 'CD3CO2CH3' from CH3OCO-C6H4-(N) over bar COCD3. Major processes involve (i) losses of radicals to form stable radical anions, e.g. loss of a ring hydrogen atom and losses from the ester (CH3 ., CH3O . and . CO2CH3), (ii) losses of neutral molecules from the amide moiety [e.g. CO (R = H) and CH2CO (R = CH3), and proximity effects when the two substituents are ortho [e.g. loss of (CH3OD+CO2) from o-CH3OCO-C6H4 (N) over bar COCD3].

Unusual cross-ring SN2 reactions of [MH]− ions of methoxyacetanilides

Deprotonated o, m-, and p-methoxyacetanilide show pronounced peaks in their collision-induced tandem mass spectra (MS/MS) produced by losses of the elements of C2H6. It is proposed that this reaction is a 'cross-ring' internal S(N)2 reaction involving an incipient methyl anion. For example, p-CH3O-C6H4-N--CO-CH3--> [(p.CH3O-C6H4-N=C=O)CH3-]--> O---C6H4-N=C=O+C2H6.

Self-determination, control, and reactions to changes in workload : a work simulation

The objective of this experimental study is to capture the dynamic temporal processes that occur in changing work settings and to test how work control and individuals' motivational predispositions interact to predict reactions to these changes. To this aim, we examine the moderating effects of global self-determined and non-self-determined motivation, at different levels of work control, on participants' adaptation and stress reactivity to changes in workload during four trials of an inbox activity. Workload was increased or decreased at Trial 3, and adaptation to this change was examined via fluctuations in anxiety, coping, motivation, and performance. In support of the hypotheses, results revealed that, for non-self-determined individuals, low work control was stress-buffering and high work control was stress-exacerbating when predicting anxiety and intrinsic motivation. In contrast, for self-determined individuals, high work control facilitated the adaptive use of planning coping in response to a change in workload. Overall, this pattern of results demonstrates that, while high work control was anxiety-provoking and demotivating for non-self-determined individuals, self-determined individuals used high work control to implement an adaptive antecedent-focused emotion regulation strategy (i.e., planning coping) to meet situational demands. Other interactive effects of global motivation emerged on anxiety, active coping, and task performance. These results and their practical implications are discussed.

General self-efficacy influences affective task reactions during a work simulation : the temporal effects of changes in workload at different levels of control

This study investigated the effects of workload, control, and general self-efficacy on affective task reactions (i.e., demands-ability fit, active coping, and anxiety) during a work simulation. The main goals were: (1) to determine the extent general self-efficacy moderates the effects of demand and control on affective task reactions, and; (2) to determine if this varies as a function of changes in workload. Participants (N=141) completed an inbox activity under conditions of low or high control and within low and high workload conditions. The order of trials varied so that workload increased or decreased. Results revealed individuals with high general self-efficacy reported better demands-abilities fit and active coping as well as less anxiety. Three interactive effects were found. First, it was found that high control increased demands-abilities fit from trial 1 to trial 2, but only when workload decreased. Second, it was found that low efficacious individuals active coping increased in trial 2, but only under high control. Third, it was found that high control helped high efficacious individuals manage anxiety when workload decreased. However, for individuals with low general self-efficacy, neither high nor low control alleviated anxiety (i.e., whether workload increased or decreased over time).

Base-induced decomposition of alkyl hydroperoxides in the gas phase. Part 3. Kinetics and dynamics in HO-+CH3OOH, C2H5OOH, and tert-C4H9OOH reactions

The E-CO(2) elimination reactions of alkyl hydroperoxides proceed via abstraction of an (x-hydrogen by a base: X- + (RRHCOOH)-R-1-H-2 -> HX + (RRC)-R-1-C-2=O + HO-. Efficiencies and product distributions for the reactions of the hydroxide anion with methyl, ethyl, and tert-butyl hydroperoxides are studied in the gas phase. On the basis of experiments using three isotopic analogues, HO- + CH3OOH, HO- + CD3OOH, and H18O- + CH3OOH. the overall intrinsic reaction efficiency is determined to be 80% or greater. The E(CO)2 decomposition is facile for these methylperoxide reactions, and predominates over competing proton transfer at the hydroperoxide moiety. The CH3CH2OOH reaction displays a similar E(CO)2 reactivity, whereas proton transfer and the formation of HOO- are the exclusive pathways observed for (CH3)(3)COOH, which has no (x-hydrogen. All results are consistent with the E-CO(2) mechanism, transition state structure, and reaction energy diagrams calculated using the hybrid density functional B3LYP approach. Isotope labeling for HO- + CH3OOH also reveals some interaction between H2O and HO- within the E(CO)2 product complex [H2O center dot center dot center dot CH2=O center dot center dot center dot HO-]. There is little evidence, however. for the formation of the most exothermic products H2O + CH2(OH)O-, which would arise from nuclephilic condensation of CH2=O and HO-. The results suggest that the product dynamics are not totally statistical but are rather direct after the E-CO(2) transition state. The larger HO- + CH3CH2OOH system displays more statistical behavior during complex dissociation.

Reactions of the hydroperoxide anion with dimethyl methylphosphonate in an ion trap mass spectrometer : evidence for a gas phase alpha-effect

The gas phase degradation reactions of the chemical warfare agent (CWA) simulant, dimethyl methylphosphonate (DMMP), with the hydroperoxide anion (HOO(-)) were investigated using a modified quadrupole ion trap mass spectrometer. The HOO(-) anion reacts readily with neutral DMMP forming two significant product ions at m/z 109 and m/z 123. The major reaction pathways correspond to (i) the nucleophilic substitution at carbon to form \[CH(3)P(O)(OCH(3))O](-) (m/z 109) in a highly exothermic process and (ii) exothermic proton transfer. The branching ratios of the two reaction pathways, 89% and 11% respectively, indicate that the former reaction is significantly faster than the latter. This is in contrast to the trend for the methoxide anion with DMMP, where proton transfer dominates. The difference in the observed reactivities of the HOO(-) and CH(3)O(-) anions can be considered as evidence for an a-effect in the gas phase and is supported by electronic structure calculations at the B3LYP/aug-cc-pVTZ//B3LYP/6-31+G(d) level of theory that indicate the S(N)2(carbon) process has an activation energy 7.8 kJ mol(-1) lower for HOO(-) as compared to CH(3)O(-). A similar alpha-effect was calculated for nucleophilic addition-elimination at phosphorus, but this process an important step in the perhydrolysis degradation of CWAs in solution - was not observed to occur with DMMP in the gas phase. A theoretical investigation revealed that all processes are energetically accessible with negative activation energies. However, comparison of the relative Arrhenius pre-exponential factors indicate that substitution at phosphorus is not kinetically competitive with respect to the S(N)2(carbon) and deprotonation processes.

Ion-molecule reactions of O,S-Dimethyl methylphosphonothioate : Evidence for intramolecular sulfur oxidation during VX perhydrolysis

The alkaline perhydrolysis of the nerve agent O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate (VX) was investigated by studying the ion-molecule reactions of HOO(-) with O,S-dimethyl methylphosphonothioate in a modified linear ion-trap mass spectrometer. In addition to simple proton transfer, two other abundant product ions are observed at m/z 125 and 109 corresponding to the S-methyl methylphosphonothioate and methyl methylphosphonate anions, respectively. The structure of these product ions is demonstrated by a combination of collision-induced dissociation and isotope-labeling experiments that also provide evidence for their formation by nucleophilic reaction pathways, namely, (i) S(N)2 at carbon to yield the S-methyl methylphosphonothioate anion and (ii) nucleophilic addition at phosphorus affording a reactive pentavalent intermediate that readily undergoes internal sulfur oxidation and concomitant elimination of CH(3)SOH to yield the methyl methylphosphonate anion. Consistent with previous Solution phase observations of VX perhydrolysis, the toxic P-O cleavage product is not observed in this VX model system and theoretical calculations identify P-O cleavage to be energetically uncompetitive. Conversely, intramolecular sulfur oxidation is calculated to be extremely exothermic and kinetically accessible explaining its competitiveness with the facile gas phase proton transfer process. Elimination of a sulfur moiety deactivates the nerve agent VX and thus the intramolecular sulfur oxidation process reported here is also able to explain the selective perhydrolysis of the nerve agent to relatively nontoxic products.

New approaches to the synthesis of strapped porphyrin containing bipyridinium [2]rotaxanes

Inspired by the interesting photo- and electrochemical properties observed in bipyridinium and porphyrin containing interlocked catenanes, herein we describe new approaches towards the synthesis of related rotaxanes. Previous efforts in this domain had been hampered by the limited range of chemical reactions that are compatible with these motifs, however the use of a “click” methodology, together with a better understanding of the size of these strapped porphyrin macrocycles, resulted in the synthesis of a bipyridinium porphyrin [2]rotaxane in modest yields. X-ray crystallography of the zinc metalloporphyrin macrocycle used in this study revealed that in the solid state, these strapped porphyrins adopt a 1-dimensional coordination polymer, in which an oxygen atom in the strap of one macrocycle is coordinated to the zinc metal center in an adjacent porphyrin ring

A natural oil-based emulsion containing allantoin versus aqueous cream for managing radiation-induced skin reactions in patients with cancer : a phase III double-blind randomised controlled trial

Purpose To investigate the effects of a natural oil-based emulsion containing allantoin versus aqueous cream for preventing and managing radiation induced skin reactions (RISR). Methods and Materials A total of 174 patients were randomised and participated in the study. Patients either received Cream 1 (the natural oil-based emulsion containing allantoin) or Cream 2 (aqueous cream). Skin toxicity, pain, itching and skin-related quality of life scores were collected for up to four weeks after radiation treatment. Results Patients who received Cream 1 had a significantly lower average level of Common Toxicity Criteria at week 3 (p<0.05), but had statistically higher average levels of skin toxicity at weeks 7, 8 and 9 (all p<0.001). Similar results were observed when skin toxicity was analysed by grades. With regards to pain, patients in the Cream 2 group had a significantly higher average level of worst pain (p<0.05) and itching (p=0.046) compared to the Cream 1 group at week 3, however these differences were not observed at other weeks. In addition, there was a strong trend for Cream 2 to reduce the incidence of grade 2 or more skin toxicity in comparison to Cream 1 (p=0.056). Overall, more participants in the Cream 1 group were required to use another topical treatment at weeks 8 (p=0.049) and 9 (p=0.01). Conclusion The natural oil-based emulsion containing allantoin appears to have similar effects for managing skin toxicity compared to aqueous cream up to week 5, however, it becomes significantly less effective at later weeks into the radiation treatment and beyond treatment completion (week 6 and beyond). There were no major differences in pain, itching and skin-related quality of life. In light of these results, clinicians and patients can base their decision on costs and preferences. Overall, aqueous cream appears to be a more preferred option.

Myopic anisometropia : ocular characteristics and aetiological considerations

Anisometropia represents a unique example of ocular development, where the two eyes of an individual, with an identical genetic background and seemingly subject to identical environmental influences, can grow asymmetrically to produce significantly different refractive errors. This review provides an overview of the research examining myopic anisometropia, the ocular characteristics underlying the condition and the potential aetiological factors involved. Various mechanical factors are discussed, including corneal structure, intraocular pressure and forces generated during near work that may contribute to development of anisomyopia. Potential visually guided mechanisms of unequal ocular growth are also explored, including the influence of astigmatism, accommodation, higher-order aberrations and the choroidal response to altered visual experience. The association between binocular vision, ocular dominance and asymmetric refraction is also considered, along with a review of the genetic contribution to the aetiology of myopic anisometropia. Despite a significant amount of research into the biomechanical, structural and optical characteristics of anisometropic eyes, there is still no unifying theory, which adequately explains how two eyes within the same visual system grow to different endpoints.

Imaging of the asymmetric DC discharge: visualization to adjust plasma in the novel PECVD reactor

Normal asymmetric glow dc discharge in the thermal furnace converted into the efficient PECVD system was imaged to adjust the structure of the plasma column to the two possible localizations of the process zone. The visualization revealed the possibility to use short and long discharge configurations for the plasma-enabled growth and processing of various nanostructures in the modified setup. Images of the discharge in the two localizations are presented.

Postmodern Theory and the Choreography of Michael Clark

This study addresses two interrelated questions: Can postmodern ‘theory’ illuminate an understanding of Michael Clark’s work? and, a sub-question, In which ways, if at all, does Clark’s work demonstrate a postmodern sensibility? Chapter one, the introduction to this study, provides a ‘portrait’ of postmodernism, that is, it addresses the question What is postmodernism? Chapter two is a biography of Michael Clark. The seminal sections to this study, however, are chapters three and four. Here the author blends a discussion of a) subject matter, treatment and meanings in Clark’s choreography, b) journalistic criticisms of those features of his work, and c) postmodern theory. The outcome of these chapters is to demonstrate that Clark’s works do indeed require re-interpretation and re-evaluation, and to illustrate how these factors might be achieved.

License scheme : an optimal waste management policy under asymmetric information

A system requiring a waste management license from an enforcement agency has been introduced in many countries. A license system is usually coupled with fines, a manifest, and a disposal tax. However, these policy devices have not been integrated into an optimal policy. In this paper we derive an optimal waste management policy by using those policy devices. Waste management policies are met with three difficult problems: asymmetric information, the heterogeneity of waste management firms, and non-compliance by waste management firms and waste disposers. The optimal policy in this paper overcomes all three problems.