Development of Stimulus-Responsive Ligands for the Modulation of Copper and Iron Coordination

The ability to manipulate the coordination chemistry of metal ions has significant ramifications for the study and treatment of metal-related health concerns, including iron overload, UV skin damage, and microbial infection among many other conditions. To address this concern, chelating agents that change their metal binding characteristics in response to external stimuli have been synthesized and characterized by several spectroscopic and chromatographic analytical methods. The primary stimuli of interest for this work are light and hydrogen peroxide.

Herein we report the previously unrecognized photochemistry of aroylhydrazone metal chelator ((E)-N′-[1-(2-hydroxyphenyl)ethyliden]isonicotinoylhydrazide) (HAPI) and its relation to HAPI metal binding properties. Based on promising initial results, a series of HAPI analogues was prepared to probe the structure-function relationships of aroylhydrazone photochemistry. These efforts elucidate the tunable nature of several aroylhydrazone photoswitching properties.

Ongoing efforts in this laboratory seek to develop compounds called prochelators that exhibit a switch from low to high metal binding affinity upon activation by a stimulus of interest. In this context, we present new strategies to install multiple desired functions into a single structure. The prochelator 2-((E)-1-(2-isonicotinoylhydrazono)ethyl)phenyl (E)-3-(2,4-dihydroxyphenyl)acrylate (PC-HAPI) is masked with a photolabile trans-cinnamic acid protecting group that releases umbelliferone, a UV-absorbing, antioxidant coumarin along with a chelating agent upon UV irradiation. In addition to the antioxidant effects of the coumarin, the released chelator (HAPI) inhibits metal-catalyzed production of damaging reactive oxygen species. Finally a peroxide-sensitive prochelator quinolin-8-yl (Z)-3-(4-hydroxy-2-((4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzyl)oxy)phenyl)acrylate (BCQ) has been prepared using a novel synthetic route for functionalized cis-cinnamate esters. BCQ uses a novel masking strategy to trigger a 90-fold increase in fluorescence emission, along with the release of a desired chelator, in the presence of hydrogen peroxide.

Cannibal Animal Games: A new variant of Tic-Tac-Toe

This paper presents a new partial two-player game, called the cannibal animal game, which is a variant of Tic-Tac-Toe. The game is played on the infinite grid, where in each round a player chooses and occupies free cells. The first player Alice can occupy a cell in each turn and wins if she occupies a set of cells, the union of a subset of which is a translated, reflected and/or rotated copy of a previously agreed upon polyomino P (called an animal). The objective of the second player Bob is to prevent Alice from creating her animal by occupying in each round a translated, reflected and/or rotated copy of P. An animal is a cannibal if Bob has a winning strategy, and a non-cannibal otherwise. This paper presents some new tools, such as the bounding strategy and the punching lemma, to classify animals into cannibals or non-cannibals. We also show that the pairing strategy works for this problem.

Efficient energy distribution in a smart grid using multi-player games

info:eu-repo/semantics/submittedForPublication

Idiotypic games within the immune network.

In this paper, we have considered the problem of selection of available repertoires. With Ab2 as immunogens, we have used the idiotypic cascade to explore potential repertoires. Our results suggest that potential idiotypic repertoires are more or less the same within a species or between different species. A given idiotype "à la Oudin" can become a recurrent one within the same outbred species or within different species. Similarly, an intrastrain crossreactive idiotype can be induced in other strains, even though there is a genetic disparity between these strains. The structural basis of this phenomenon has been explored. We next examined results showing the loss and gain of recurrent idiotypes without any intentional idiotypic manipulation. A recurrent idiotype can be lost in a syngeneic transfer and a private one can become recurrent by changing the genetic background. The change of available idiotypic repertoires at the B cell level has profound influences on the idiotypic repertoires of suppressor T cells. All these results imply that idiotypic games are played by the immune system itself, a strong suggestion that the immune system is a functional idiotypic network.

[Book review] Theory of Games and Economic Behaviour

Tony Mann provides a review of the book: Theory of Games and Economic Behavior, John von Neumann and Oskar Morgenstern, Princeton University Press, 1944.

The Olympic Games and urban displacement: the case of Beijing

Urban spectacles such as the Olympic Games have been long perceived as being able to impose desired effects in the city that act as host. This kind of urban boost may include the creation of new jobs and revenue for local community, growth in tourism and convention business, improvements to city infrastructure and environment, and the stimulation of broad reform in the social, political and institutional realm. Nevertheless at the other end of the debate, the potentially detrimental impacts of Olympic urban development, particularly on disadvantaged and vulnerable groups, have also been increasingly noticed in recent years and subsequently cited by a number of high profile anti-Olympic groups to campaign against Olympic bids and awards. The common areas of concern over Olympic-related projects include the cost and debts risk, environmental threat, the occurrence of social imbalance, and disruption and disturbance of existing community life. Among these issues, displacement of low income households and squatter communities resulting from Olympic-inspired urban renewal are comparatively under-explored and have emerged as an imperative area for research inquiry. This is particularly the case where many other problems have become less prominent. Changing a city’s demographic landscape, particularly displacing lower income people from the area proposed for a profitable development is a highly contentious matter in its own right. Some see it as a natural and inevitable outgrowth of the process of urban evolution, without which cities cannot move towards a more attractive location for consumption-based business. Others believe it reflects urban crises and conflicts, highlighting the market failures, polarization and injustice. Regardless of perception,these phenomena are visible everywhere in post-industrial cities and particularly cannot be ignored when planning for the Olympic Games and other mega-events. The aim of this paper is to start the process of placing the displacement issue in the context of Olympic preparation and to seek a better understanding of their interrelations. In order to develop a better understanding of this issue in terms of cause, process, influential factors and its implication on planning policy, this paper studies the topic from both theoretic and empirical angles. It portrays various situations where the Olympics may trigger or facilitate displacement in host cities during the preparation of the Games, identifies several major variables that may affect the process and the overall outcome, and explores what could be learnt in generic terms for planning Olympic oriented infrastructure so that ill-effects to the local community can be effectively controlled. The paper concludes that the selection of development sites, the integration of Olympic facilities with the city’s fabric, the diversity of housing type produced for local residents and the dynamics of the new socioeconomic structure.

Performance assessment in serious games: Compensating for the effects of randomness

This paper is about performance assessment in serious games. We conceive serious gaming as a process of player-lead decision taking. Starting from combinatorics and item-response theory we provide an analytical model that makes explicit to what extent observed player performances (decisions) are blurred by chance processes (guessing behaviors). We found large effects both theoretically and practically. In two existing serious games random guess scores were found to explain up to 41% of total scores. Monte Carlo simulation of random game play confirmed the substantial impact of randomness on performance. For valid performance assessments, be it in-game or post-game, the effects of randomness should be included to produce re-calibrated scores that can reasonably be interpreted as the players´ achievements.

Making sense of game based user data: learning analytics in applied games

Digital learning games are useful educational tools with high motivational potential. With the application of games for instruction there comes the need of acknowledging learning game experiences also in the context of educational assessment. Learning analytics provides new opportunities for supporting assessment in and of educational games. We give an overview of current learning analytics methods in this field and reflect on existing challenges. An approach of providing reusable software assets for interaction assessment and evaluation in games is presented. This is part of a broader initiative of making available advanced methodologies and tools for supporting applied game development.

Evaluation of Serious Games: A Holistic Approach

Digital games constitute a major emerging technology that is expected to enter mainstream educational use within a few years. The highly engaging and motivating character of such games bears great potential to support immersive, meaningful, and situated learning experiences. To seize this potential, meaningful quality and impact measurements are indispensible. Although there is a growing body of evidence on the efficacy of games for learning, evaluation is often poorly designed, incomplete, biased, if not entirely absent. Well-designed evaluations demonstrating the educational effect as well as the return on investment of serious games may foster broader adoption by educational institutions and training providers, and support the development of the serious game industry. The European project RAGE introduces a comprehensive and multi-perspective framework for serious game evaluation, which is presented in this paper.

Ring-opening polymerisation of silver-diphosphine [M2L3] coordination cages to give [M2L3](infinity) coordination polymers

[M2L3] coordination cages and linear [M2L3]infinity polymers of the rigid, bridging diphosphines bis(diphenylphosphino)acetylene (dppa) and trans-1,2-bis(diphenylphosphino)ethylene (dppet) with silver(I) salts have been investigated in the solution and solid states. Unlike flexible diphosphines, 1:1 dppa/AgX mixtures do not selectively form discrete [Ag2(diphos)2(X)2] macrocycles; instead dynamic mixtures of one-, two- and three-coordinate complexes are formed. However, 3:2 dppa/AgX ratios (X = SbF6. BF4, O3SCF3 or NO3) do lead selectively to new [M2L3] triply bridged cage complexes [Ag2(dppa)3(X)2] 1a-d (X = SbF6 a, BF4 b, O3SCF3 c, NO3 d), which do not exhibit Ag-P bond dissociation at room temperature on the NMR time scale (121 MHz). Complexes la-d were characterised by X-ray crystallography and were found to have small internal cavities, helical conformations and multiple intramolecular aromatic interactions. The nucleophilicity of the anion subtly influences the cage shape: Increasing nucleophilicity from SbF6 (1a) through BF4 (1b) and O3SCF3 (1c) to NO3 (1d) increases the pyramidal distortion at the AgP3 centres, stretching the cage framework (with Ag...Ag distances increasing from 5.48 in 1a to 6.21 A in 1d) and giving thinner internal cavities. Crystal packing strongly affected the size of the helical twist angle, and no correlation between this parameter and the Ag-Ag distance was observed. When crystalline 1c was stored in its supernatant for 16 weeks, conversion occured to the isostoichiometric [M2L3]infinity coordination polymer [Ag(dppa)2Ag(dppa)(O3SCF3)2]infinity (1c'). X-ray crystallography revealed a structure with ten-membered Ag2(dppa)2 rings linked into infinite one-dimensional chains by a third dppa unit. The clear structural relationship between this polymer and the precursor cage 1c suggests a novel example of ring-opening polymerisation. With dppet, evidence for discrete [M2L3] cages was also found in solution, although 31P NMR spectroscopy suggested some Ag-P bond dissociation. On crystallisation, only the corresponding ring-opened polymeric structures [M2L3]infinity could be obtained. This may be because the greater steric bulk of dppet versus dppa destabilises the cage and favours the ring-opening polymerisation.

Modelling relative motion to facilitate intra-limb coordination

The importance of relative motion information when modelling a novel motor skill was examined. Participants were assigned to one of four groups. Groups 1 and 2 viewed demonstrations of a skilled cricket bowler presented in either video or point light format. Group 3 observed a single point of light pertaining to the wrist of the skilled bowler only. Participants in Group 4 did not receive a demonstration and acted as controls. During 60 acquisition trials, participants in the demonstration groups viewed a model five times before each 10-trial block. Retention was examined the following day. Intra-limb coordination was assessed for the right elbow relative to the wrist in comparison to the model. The demonstration groups showed greater concordance with the model than the control group. However, the wrist group performed less like the model than the point light and video groups, who did not differ from each other. These effects were maintained in retention. Relative motion information aided the acquisition of intra-limb coordination, while making this information more salient (through point lights) provided no additional benefit. The motion of the models bowling arm was replicated more closely than the non-bowling arm, suggesting that information from the end-effector is prioritized during observation for later reproduction.