Isolation and characterization of charge-tagged phenylperoxyl radicals in the gas phase : direct evidence for products and pathways in low temperature benzene oxidation

The phenylperoxyl radical has long been accepted as a critical intermediate in the oxidation of benzene and an archetype for arylperoxyl radicals in combustion and atmospheric chemistry. Despite being central to many contemporary mechanisms underpinning these chemistries, reports of the direct detection or isolation of phenylperoxyl radicals are rare and there is little experimental evidence connecting this intermediate with expected product channels. We have prepared and isolated two charge-tagged phenyl radical models in the gas phase [i.e., 4-(N,N,N-trimethylammonium) phenyl radical cation and 4-carboxylatophenyl radical anion] and observed their reactions with dioxygen by ion-trap mass spectrometry. Measured reaction rates show good agreement with prior reports for the neutral system (k(2)[(Me3N+)C6H4 center dot + O-2] = 2.8 x 10(-11) cm(3) molecule(-1) s(-1), Phi = 4.9%; k(2)[(-O2C)C6H4 center dot + O-2] = 5.4 x 10(-1)1 cm(3) molecule(-1) s(-1), Phi = 9.2%) and the resulting mass spectra provide unequivocal evidence for the formation of phenylperoxyl radicals. Collisional activation of isolated phenylperoxyl radicals reveals unimolecular decomposition by three pathways: (i) loss of dioxygen to reform the initial phenyl radical; (ii) loss of atomic oxygen yielding a phenoxyl radical; and (iii) ejection of the formyl radical to give cyclopentadienone. Stable isotope labeling confirms these assignments. Quantum chemical calculations for both charge-tagged and neutral phenylperoxyl radicals confirm that loss of formyl radical is accessible both thermodynamically and entropically and competitive with direct loss of both hydrogen atom and carbon dioxide.

Exploring a biomimicry based approach and key barriers to evolving water infrastructure systems

Access to clean water is essential for human life and a critical issue facing much of modern society, especially as a result of the 21st Century triad of challenges – population growth, resource scarcity and pollution – which contribute to the rising complexity of providing adequate access to this essential resource for large parts of society. As such, there is now an increasing need for innovative solutions to source, treat and distribute water to cities across the globe. This position paper explores biomimicry – emulating natural form, function, process and systems – as an alternative and sustainable design approach to traditional water infrastructure systems. The key barriers to innovations such as biomimicry are summarised, indicating that regulatory and economic grounds are some of the major hindrances to integrating alternative design approaches in the water sector in developed countries. This paper examines some of the benefits of moving past these barriers to develop sustainable, efficient and resilient solutions that provide adequate access to water in the face of contemporary challenges.

Evolving a design driven ‘hybrid’ research approach to inform and advance sustainable outcomes in the built environment sector

A significant reduction in global greenhouse gas (GHG) emissions is a priority, and the preservation of existing building stock presents a significant opportunity to reduce the carbon footprint of our built environment. Within this ‘wicked’ problem context, and moving beyond the ad hoc and incremental performance improvements that have been made to date, collaborative and multidisciplinary efforts are required to find rapid and transformational solutions. Design has emerged as a strategic and redirective practice, and lessons can therefore be learned about transformation and potentially applied in the built environment. The purpose of this paper is to discuss a pragmatic and novel research approach for undertaking such applied design driven research. This paper begins with a discussion of key contributions from design science (rational) and action research (reflective) philosophies in creating an emerging methodological ‘hybrid design approach’. This research approach is then discussed in relation to its application to specific research exploring the processes, methods and lessons from design in heritage building retrofit projects. Drawing on both industry and academic knowledge to ensure relevance and rigour, it is anticipated that the hybrid design approach will be useful for others tackling such complex wicked problems that require context-specific solutions.

Effects of dissolved oxygen availability and culture biomass at induction upon the intracellular expression of monoamine oxidase by recombinant E. coli in fed batch bioprocesses

The effects of oxygen availability and induction culture biomass upon production of an industrially important monoamine oxidase (MAO) were investigated in fed-batch cultures of a recombinant E. coli. For each induction cell biomass 2 different oxygenation methods were used, aeration and oxygen enriched air. Induction at higher biomass levels increased the culture demand for oxygen, leading to fermentative metabolism and accumulation of high levels of acetate in the aerated cultures. Paradoxically, despite an almost eight fold increase in acetate accumulation to levels widely reported to be highly detrimental to protein production, when induction wet cell weight (WCW) rose from 100% to 137.5%, MAO specific activity in these aerated processes showed a 3 fold increase. By contrast, for oxygenated cultures induced at WCW's 100% and 137.5% specific activity levels were broadly similar, but fell rapidly after the maxima were reached. Induction at high biomass levels (WCW 175%) led to very low levels of specific MAO activity relative to induction at lower WCW's in both aerated and oxygenated cultures. Oxygen enrichment of these cultures was a useful strategy for boosting specific growth rates, but did not have positive effects upon specific enzyme activity. Based upon our findings, consideration of the amino acid composition of MAO and previous studies on related enzymes, we propose that this effect is due to oxidative damage to the MAO enzyme itself during these highly aerobic processes. Thus, the optimal process for MAO production is aerated, not oxygenated, and induced at moderate cell density, and clearly represents a compromise between oxygen supply effects on specific growth rate/induction cell density, acetate accumulation, and high specific MAO activity. This work shows that the negative effects of oxygen previously reported in free enzyme preparations, are not limited to these acellular environments but are also discernible in the sheltered environment of the cytosol of E. coli cells.

The Service Portfolio of a BPM Center of Excellence

A key concept for the centralized provision of Business Process Management (BPM) is the Center of Excellence (CoE). Organizations establish a CoE (aka BPM Support Office) as their BPM maturity increases in order to ensure a consistent and cost-effective way of offering BPM services. The definition of the offerings of such a center and the allocation of roles and responsibilities play an important role within BPM Governance. In order to plan the role of such a BPM CoE, this chapter proposes the productization of BPM leading to a set of fifteen distinct BPM services. A portfolio management approach is suggested to position these services. The approach allows identifying specific normative strategies for each BPM service, such as further training or BPM communication and marketing. A public sector case study provides further insights into how this approach has been used in practice. Empirical evidence from a survey with 15 organizations confirms the coverage of this set of BPM services and shows typical profiles for such BPM Centers of Excellence.

Concerted HO2 elimination from alpha-Aminoalkylperoxyl free radicals : Experimental and theoretical evidence from the gas phase NH2 center dot CHCO2- + O-2 reaction

We have investigated the gas-phase reaction of the alpha-aminoacetate (glycyl) radical anion (NH2(sic)CHCO2-) with O-2 using ion trap mass spectrometry, quantum chemistry, and statistical reaction rate theory. This radical is found to undergo a remarkably rapid reaction with O-2 to form the hydroperoxyl radical (HO2(sic)) and an even-electron imine (NHCHCO2-), with experiments and master equation simulations revealing that reaction proceeds at the ion molecule collision rate. This reaction is facilitated by a low-energy concerted HO2(sic) elimination mechanism in the NH2CH(OO(sic))CO2- peroxyl radical. These findings can explain the widely observed free-radical-mediated oxidation of simple amino acids to amides plus alpha-keto acids (their imine hydrolysis products). This work also suggests that imines will be the main intermediates in the atmospheric oxidation of primary and secondary amines, including amine carbon capture solvents such as 2-aminoethanol (commonly known as monoethanolamine, or MEA), in a process that avoids the ozone-promoting conversion of (sic)NO to (sic)NO2 commonly encountered in peroxyl radical chemistry.

Photoelectron spectroscopic study of the oxyallyl diradical

The photoelectron spectrum of the oxyallyl (OXA) radical anion has been measured. The radical anion has been generated in the reaction of the atomic oxygen radical anion (O center dot-) with acetone. Three low-lying electronic states of OXA have been observed in the spectrum. Electronic structure calculations have been performed for the triplet states (B-3(2) and B-3(1)) of OXA and the ground doublet state ((2)A(2)) of the radical anion using density, functional theory (DFT). Spectral simulations have been carried out for the triplet statics based on the results of the DFT calculations. The simulation identifies a vibrational progression of the CCC bending mode of the B-3(2) state of OXA in the lower electron binding energy (eBE) portion of the spectrum. On top of the B-3(2) feature, however, the experimental spectrum exhibits additional photoelectron peaks whose angular distribution is distinct from that for the vibronic peaks of the B-3(2) state. Complete active space self-consistent field (CASSCF) method and second-order perturbation theory based on the CASSCF wave function (CASPT2) have been employed to study the lowest singlet state ((1)A(1)) of OXA. The simulation based on the results of these electronic structure calculations establishes that the overlapping peaks represent the vibrational ground level of the (1)A(1) state and its vibrational progression of the CO stretching mode. The A, state is the lowest electronic state of,OXA, and the electron affinity (EA) of OXA is 1.940 +/- 0.010 eV. The B-3(2) state is the first excited state with an electronic term energy of 55 +/- 2 meV. The widths of the vibronic peaks of the (X) over tilde (1)A(1) state are much broader than those of the (a) over tilde B-3(2) state, implying that the (1)A(1) state is indeed a transition state. The CASSCF and CASPT2 calculations suggest that the (1)A(1) state is at a potential maximum along the nuclear coordinate representing disrotatory motion of the two methylene groups, which leads to three-membered-ring formation, i.e., cydopropanone. The simulation of (b) over tilde B-3(1) OXA reproduces the higher eBE portion of the spectrum very well. The term energy of the B-3(1) state is 0.883 +/- 0.012 eV. Photoelectron spectroscopic measurements have also been conducted for the other ion products of the O center dot- reaction with acetone. The photoelectron imaging spectrum of the acetylcarbene (AC) radical anion exhibits a broad, structureless feature, which is assigned to the (X) over tilde (3)A '' state of AC. The ground ((2)A '') and first excited ((2)A') states of the 1-methylvinoxy (1-MVO) radical have been observed in the photoelectron spectrum of the 1-MVO ion, and their vibronic structure has been analyzed.

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

Auditor communication in an evolving environment : going beyond SAS 600 auditors' reports on financial statements

In 1993 the Auditing Practices Board issued an expanded audit report, SAS 600 Auditors’ Reports on Financial Statements, in an attempt to educate users and to clarify certain matters pertaining to the audit function. This paper investigates the extent to which the new audit report, SAS 600, has been successful in aligning the views of auditors, preparers and users about issues dealt with in the expanded audit report, and the extent to which the three groups considered that it would be useful for additional matters, including corporate governance, to be reported upon by the auditor. Our findings suggest that SAS 600 has been successful in clarifying the purpose of the audit and the respective responsibilities of auditors and directors. However, to meet the expectations of users and to add more value, the audit report needs to provide more information about the findings of the audit.

What contribution can International Relations make to the evolving global health agenda?

This article presents two approaches that have dominated International Relations in their approach to the international politics of health. The statist approach, which is primarily security-focused, seeks to link health initiatives to a foreign or defence policy remit. The globalist approach, in contrast, seeks to advance health not because of its intrinsic security value but because it advances the well-being and rights of individuals. This article charts the evolution of these approaches and demonstrates why both have the potential to shape our understanding of the evolving global health agenda. It examines how the statist and globalist perspectives have helped shape contemporary initiatives in global health governance and suggests that there is evidence of an emerging convergence between the two perspectives. This convergence is particularly clear in the articulation of a number of UN initiatives in this area—especially the One World, One Health Strategic Framework and the Oslo Ministerial Declaration (2007) which inspired the first UN General Assembly resolution on global health and foreign policy in 2009 and the UN Secretary-General's note ‘Global health and foreign policy: strategic opportunities and challenges'. What remains to be seen is whether this convergence will deliver on securing states’ interest long enough to promote the interests of the individuals who require global efforts to deliver local health improvements.

See to believe : the Center for Tactical Magic’s sleight of hand

The Bay Area’s Center for Tactical Magic has been performing ‘‘magical’’ art interventions since 2000. The Center’s work augments traditional activist techniques by offering new conceptions of what art and activism can entail in a contemporary urban context. This article explores how Jacques Rancie`re’s reconfigured relationship between art and politics can be applied to the Center’s work, providing new distributions of the sensible for participants.

Tuning of magnetization in vertical graphenes by plasma-enabled chemical conversion of organic precursors with different oxygen content

Different magnetization in vertical graphenes fabricated by plasma-enabled chemical conversion of organic precursors with various oxygen atom contents and bonding energies was achieved. The graphenes grown from fat-like precursors exhibit magnetization up to 8 emu g−1, whereas the use of sugar-containing precursors results in much lower numbers. A relatively high Curie temperature exceeding 600 K was also demonstrated.

Plasma enables edge-to-center-oriented graphene nanoarrays on Si nanograss

The formation of clearly separated vertical graphenenanosheets on silicon nanograss support is demonstrated. The plasma-enabled, two-stage mask-free process produced self-organized vertical graphenes of a few carbon layers (as confirmed by advanced microanalysis), prominently oriented in the substrate center–substrate edge direction. It is shown that the width of the alignment zone depends on the substrate conductivity, and thus the electric field in the vicinity of the growth surface is responsible for the graphene alignment. This finding is confirmed by the Monte Carlo simulations of the ion flux distribution in the silicon nanograss pattern.