UV Photodissociation Action Spectroscopy of Haloanilinium Ions in a Linear Quadrupole Ion Trap Mass Spectrometer

UV-vis photodissociation action spectroscopy is becoming increasingly prevalent because of advances in, and commercial availability of, ion trapping technologies and tunable laser sources. This study outlines in detail an instrumental arrangement, combining a commercial ion-trap mass spectrometer and tunable nanosecond pulsed laser source, for performing fully automated photodissociation action spectroscopy on gas-phase ions. The components of the instrumentation are outlined, including the optical and electronic interfacing, in addition to the control software for automating the experiment and performing online analysis of the spectra. To demonstrate the utility of this ensemble, the photodissociation action spectra of 4-chloroanilinium, 4-bromoanilinium, and 4-iodoanilinium cations are presented and discussed. Multiple photoproducts are detected in each case and the photoproduct yields are followed as a function of laser wavelength. It is shown that the wavelength-dependent partitioning of the halide loss, H loss, and NH3 loss channels can be broadly rationalized in terms of the relative carbon-halide bond dissociation energies and processes of energy redistribution. The photodissociation action spectrum of (phenyl)Ag-2 (+) is compared with a literature spectrum as a further benchmark.

Ultraviolet Photodissociation of the N-Methylpyridinium Ion: Action Spectroscopy and Product Characterization

The ultraviolet photodissociation of gas-phase N-methylpyridinium ions is studied at room temperature using laser photodissociation mass spectrometry and structurally diagnostic ion-molecule reaction kinetics. The C5H5N-CH3+ (m/z 94), C5H5N-CD3+ (m/z 97), and C5D5N-CH3+(m/z 99) isotopologues are investigated, and it is shown that the N-methylpyridinium ion photodissociates by the loss of methane in the 36 000 - 43 000 cm(-1) (280 - 230 nm) region. The dissociation likely occurs on the ground state surface following internal conversion from the SI state. For each isotopologue, by monitoring the photofragmentation yield as a function of photon wavenumber, a broad vibronically featured band is recorded with origin (0-0) transitions assigned at 38 130, 38 140 and 38 320 cm(-1) for C5H5N-CH3+ C5H5N-CD3+ and C5D5N-CH3+, respectively. With the aid of quantum chemical calculations (CASSCF(6,6)/aug-cc-pVDZ), most of the observed vibronic detail is assigned to two in-plane ring deformation modes. Finally, using ion-molecule reactions, the methane coproduct at m/z 78 is confirmed as a 2-pyridinylium ion.

Ultraviolet action spectroscopy of iodine labeled peptides and proteins in the gas phase

Structural investigations of large biomolecules in the gas phase are challenging. Herein, it is reported that action spectroscopy taking advantage of facile carbon-iodine bond dissociation can be used to examine the structures of large molecules, including whole proteins. Iodotyrosine serves as the active chromophore, which yields distinctive spectra depending on the solvation of the side chain by the remainder of the molecule. Isolation of the chromophore yields a double featured peak at ∼290 nm, which becomes a single peak with increasing solvation. Deprotonation of the side chain also leads to reduced apparent intensity and broadening of the action spectrum. The method can be successfully applied to both negatively and positively charged ions in various charge states, although electron detachment becomes a competitive channel for multiply charged anions. In all other cases, loss of iodine is by far the dominant channel which leads to high sensitivity and simple data analysis. The action spectra for iodotyrosine, the iodinated peptides KGYDAKA, DAYLDAG, and the small protein ubiquitin are reported in various charge states. © 2012 American Chemical Society.

Task constraints

Newell (1985, 1986) identified the importance of interacting constraints on the emergent behaviours of learners or performers in sport as they assemble functional states of movement organisation in achieving task goals. Constraints, related to the person, task and environment, were defined as ‘boundaries or features that limit motion of the entity under consideration at any moment in time’ (Newell, 1986, p.347). Personal (or organismic) constraints include factors such as individual anthropometrics (height, weight, and limb lengths), fitness (e.g., strength, speed, aerobic capacity, and flexibility), mental skills (e.g. concentration, confidence, emotional control and motivation), perceptual and decisionmaking skills (e.g., recognising patterns of play, anticipation by reading the movements of opponents) and personality factors (e.g., risk taking or conservative behaviours). Newell (1986, p.350) distinguished between general environmental constraints, such as gravity, ambient temperature, natural light and altitude and task constraints, which are task specific and concerned with the goals of a specific activity. More recently, socio-cultural constraints (e.g., family support, cultural expectations and access to facilities) have also been considered as environmental constraints. Application of the constraints framework to the study of sport performance has led to task constraints being defined to include factors such as rules of games, equipment used, boundary playing areas and markings, nets and goals, the number of...

A history of environmental management in the field in Queensland : episodes of activity

This paper reviews a wide range of literature on environmental management in the field in Queensland, and analyzes this by period and by author. An episodic pattern of activities since European settlement is evident. Periods of exploration (pre-1950) and inventory- compilation (ca. 1950-1970) were followed by two decades of media and non-government organization campaigning (ca. 1970-1990), then an era dominated by government regulatory action (ca. 1990-2010). These eras dominated public perception of what was happening in environmental practice. They were delineated by historic ‘interventions’ (summarily, the end of World War II, the 1971 inflationary crisis, and computerization respectively).

Editorial : Action research, action learning and community services

This edition of ALARj has a focus on the contribution of action learning and action research to the development of community services, particularly nonprofits. The landscape of community services has been changing rapidly in recent decades, and can be typified by the notion of complexity. Complexity in the nature of issues that services seek to respond to, complexity in the policy environment and systems of support that have tended to silo and compartmentalise problems and people, and complexity in the institutional location non-profit services occupy in ‘helping’ those who are seen as ‘in need’ or marginalised. In addition to being typified by complexity the environment in which community services are located is dynamic, undergoing profound and ongoing change as neo-liberal approaches to understanding and responding to human need, which emphasise the individualisation of risk, and market principles such as choice, competition and innovation, drive social policy. How can long held values of empowerment, care, inclusivity and benefit to individuals and communities have expression in community services as they grapple with the challenges of being viable and relevant in such a dynamically changing environment? This edition brings together a range of contributions which speak to these challenges. The thematic through these is that processes are needed which engage services and communities in ongoing processes of inquiry about how they can best proceed in contexts typified by complexity and change. Action learning and action research can provide processes of this character.

Prior storm experience moderates water surge perception and risk

Background How accurately do people perceive extreme water speeds and how does their perception affect perceived risk? Prior research has focused on the characteristics of moving water that can reduce human stability or balance. The current research presents the first experiment on people's perceptions of risk and moving water at different speeds and depths. Methods Using a randomized within-person 2 (water depth: 0.45, 0.90 m) ×3 (water speed: 0.4, 0.8, 1.2 m/s) experiment, we immersed 76 people in moving water and asked them to estimate water speed and the risk they felt. Results Multilevel modeling showed that people increasingly overestimated water speeds as actual water speeds increased or as water depth increased. Water speed perceptions mediated the direct positive relationship between actual water speeds and perceptions of risk; the faster the moving water, the greater the perceived risk. Participants' prior experience with rip currents and tropical cyclones moderated the strength of the actual–perceived water speed relationship; consequently, mediation was stronger for people who had experienced no rip currents or fewer storms. Conclusions These findings provide a clearer understanding of water speed and risk perception, which may help communicate the risks associated with anticipated floods and tropical cyclones.

Wind speed perception and risk

Background How accurately do people perceive extreme wind speeds and how does that perception affect the perceived risk? Prior research on human–wind interaction has focused on comfort levels in urban settings or knock-down thresholds. No systematic experimental research has attempted to assess people's ability to estimate extreme wind speeds and perceptions of their associated risks. Method We exposed 76 people to 10, 20, 30, 40, 50, and 60 mph (4.5, 8.9, 13.4, 17.9, 22.3, and 26.8 m/s) winds in randomized orders and asked them to estimate wind speed and the corresponding risk they felt. Results Multilevel modeling showed that people were accurate at lower wind speeds but overestimated wind speeds at higher levels. Wind speed perceptions mediated the direct relationship between actual wind speeds and perceptions of risk (i.e., the greater the perceived wind speed, the greater the perceived risk). The number of tropical cyclones people had experienced moderated the strength of the actual–perceived wind speed relationship; consequently, mediation was stronger for people who had experienced fewer storms. Conclusion These findings provide a clearer understanding of wind and risk perception, which can aid development of public policy solutions toward communicating the severity and risks associated with natural disasters.

Medium and mode : relationships between visual experience and perception in an installation arts practice

Working primarily within the natural landscape, this practice-led research project explored connections between the artist's visual and perceptual experience of a journey or place while simultaneously emphasizing the capacity for digital media to create a perceptual dissonance. By exploring concepts of time, viewpoint, duration of sequences and the manipulation of traditional constructs of stop-frame animation, the practical work created a cognitive awareness of the elements of the journey through optical sensations. The work allowed an opportunity to reflect on the nature of visual experience and its mediation through images. The project recontextualized the selected mediums of still photography, animation and projection within contemporary display modes of multiple screen installations by analysing relationships between the experienced and the perceived. The resulting works added to current discourse on the interstices between still and moving imagery in a digital world.

Teacher understandings of orientation and transition programs from action research in five schools

Discontinuity between prior-to-school and school sectors in Australia reflects an historical, philosophical and pedagogical schism. This is most evident as children transition from one sector to the other. However, contemporary international research, alongside an intensive focus on policy and practice in early years education has challenged many of the taken-for-granted assumptions that perpetuate this rift. Drawing on data collected in a recent action research project, we present evidence of how a group of primary school kindergarten teachers define differences between orientation and transition programs, understand the importance of transition and how they position themselves in this process. The absence of Australian policy mandating and guiding the work of teachers across sectors is a significant factor perpetuating discontinuity in transition practices between prior–to-school and school sectors.

Teaching fractions to adult learners enrolled in a civil construction course : knowledge, action and materials action in tandem

This paper investigates the teaching and learning of fractions to Indigenous adult learners in a Civil Construction Certificate Course. More specifically it explores why the use of materials is critical to building knowledge and understanding. This focus is important for two reasons. First, it allows for considerations of a trainer’s approach for teaching fractions and, second it provides insights into how adult learners can be supported with representing their practical experiences of fractions to make generalisation thus building on their knowledge and learning experiences. The paper draws on teaching episodes from an Australian Research Council funded Linkage project that investigates how mathematics is taught and learned in Certificate Courses, here, Certificate 11 in Civil Construction. Action research and decolonising methods (Smith, 1999) were used to conduct the research. Video excerpts which feature one trainer and three students are analysed and described. Findings from the data indicate that adult learners need to be supported with materials to assist with building their capacity to know and apply understandings of fractions in a range of contexts, besides construction. Without materials and where fractions are taught via pen and paper tasks, students are less likely to retain and apply fraction ideas to their Certificate Course. Further they are less likely to understand decimals because of limited understanding of fractions.

Output feedback optimal control with contraints

In Chapters 1 through 9 of the book (with the exception of a brief discussion on observers and integral action in Section 5.5 of Chapter 5) we considered constrained optimal control problems for systems without uncertainty, that is, with no unmodelled dynamics or disturbances, and where the full state was available for measurement. More realistically, however, it is necessary to consider control problems for systems with uncertainty. This chapter addresses some of the issues that arise in this situation. As in Chapter 9, we adopt a stochastic description of uncertainty, which associates probability distributions to the uncertain elements, that is, disturbances and initial conditions. (See Section 12.6 for references to alternative approaches to model uncertainty.) When incomplete state information exists, a popular observer-based control strategy in the presence of stochastic disturbances is to use the certainty equivalence [CE] principle, introduced in Section 5.5 of Chapter 5 for deterministic systems. In the stochastic framework, CE consists of estimating the state and then using these estimates as if they were the true state in the control law that results if the problem were formulated as a deterministic problem (that is, without uncertainty). This strategy is motivated by the unconstrained problem with a quadratic objective function, for which CE is indeed the optimal solution (˚Astr¨om 1970, Bertsekas 1976). One of the aims of this chapter is to explore the issues that arise from the use of CE in RHC in the presence of constraints. We then turn to the obvious question about the optimality of the CE principle. We show that CE is, indeed, not optimal in general. We also analyse the possibility of obtaining truly optimal solutions for single input linear systems with input constraints and uncertainty related to output feedback and stochastic disturbances.We first find the optimal solution for the case of horizon N = 1, and then we indicate the complications that arise in the case of horizon N = 2. Our conclusion is that, for the case of linear constrained systems, the extra effort involved in the optimal feedback policy is probably not justified in practice. Indeed, we show by example that CE can give near optimal performance. We thus advocate this approach in real applications.

Constrained predictive control of ship fin stabilizers to prevent dynamic stall

In moderate to high sea states, the effectiveness of ship fin stabilizers can severely deteriorate due to nonlinear effects arising from unsteady hydrodynamic characteristics of the fins: dynamic stall. These nonlinear effects take the form of a hysteresis, and they become very significant when the effective angle of attack of the fins exceeds a certain threshold angle. Dynamic stall can result in a complete loss of control action depending on how much the fins exceed the threshold angle. When this is detected, it is common to reduce the gain of the controller that commands the fins. This approach is cautious and tends to reduce performance when the conditions leading to dynamic stall disappear. An alternative approach for preventing the effects while keeping high performance, consists of estimating the effective angle of attack and set a conservative constraint on it as part of the control objectives. In this paper, we investigate the latter approach, and propose the use of a model predictive control (MPC) to prevent the development of these nonlinear effects by considering constraints on both the mechanical angle of the fins and the effective angle of attack.

Performance degradation in feedback control due to constraints

In this note, we present a method to characterize the degradation in performance that arises in linear systems due to constraints imposed on the magnitude of the control signal to avoid saturation effects. We do this in the context of cheap control for tracking step signals.