Gotowa bibliografia na temat „Multi-cage complexes”

In this paper, we report on the synthesis of novel copper(ii) complexes containing a multi-donor N,O-type ligand based on mono-substituted cage-like silsesquioxanes bound by trifunctional acyl chloride.

AbstractCoiled-coil protein origami (CCPO) is a modular strategy for the de novo design of polypeptide nanostructures. CCPO folds are defined by the sequential order of concatenated orthogonal coiled-coil (CC) dimer-forming peptides, where a single-chain protein is programmed to fold into a polyhedral cage. Self-assembly of CC-based nanostructures from several chains, similarly as in DNA nanotechnology, could facilitate the design of more complex assemblies and the introduction of functionalities. Here, we show the design of a de novo triangular bipyramid fold comprising 18 CC-forming segments and define the strategy for the two-chain self-assembly of the bipyramidal cage from asymmetric and pseudo-symmetric pre-organised structural modules. In addition, by introducing a protease cleavage site and masking the interfacial CC-forming segments in the two-chain bipyramidal cage, we devise a proteolysis-mediated conformational switch. This strategy could be extended to other modular protein folds, facilitating the construction of dynamic multi-chain CC-based complexes.

Introduction: Bubbles and Sport The ephemeral materiality of bubbles – beautiful, spectacular, and distracting but ultimately fragile – when applied to protect or conserve in the interests of sport-media profit, creates conditions that exacerbate existing inequalities in sport and society. Bubbles are usually something to watch, admire, and chase after in their brief yet shiny lives. There is supposed to be, technically, nothing inside them other than one or more gasses, and yet we constantly refer to people and objects being inside bubbles. The metaphor of the bubble has been used to describe the life of celebrities, politicians in purpose-built capital cities like Canberra, and even leftist, environmentally activist urban dwellers. The metaphorical and material qualities of bubbles are aligned—they cannot be easily captured and are liable to change at any time. In this article we address the metaphorical sporting bubble, which is often evoked in describing life in professional sport. This is a vernacular term used to capture and condemn the conditions of life of elite sportspeople (usually men), most commonly after there has been a sport-related scandal, especially of a sexual nature (Rowe). It is frequently paired with connotatively loaded adjectives like pampered and indulged. The sporting bubble is rarely interrogated in academic literature, the concept largely being left to the media and moral entrepreneurs. It is represented as involving a highly privileged but also pressurised life for those who live inside it. A sporting bubble is a world constructed for its most prized inhabitants that enables them to be protected from insurgents and to set the terms of their encounters with others, especially sport fans and disciplinary agents of the state. The Covid-19 pandemic both reinforced and reconfigured the operational concept of the bubble, re-arranging tensions between safety (protecting athletes) and fragility (short careers, risks of injury, etc.) for those within, while safeguarding those without from bubble contagion. Privilege and Precarity Bubble-induced social isolation, critics argue, encourages a loss of perspective among those under its protection, an entitled disconnection from the usual rules and responsibilities of everyday life. For this reason, the denizens of the sporting bubble are seen as being at risk to themselves and, more troublingly, to those allowed temporarily to penetrate it, especially young women who are first exploited by and then ejected from it (Benedict). There are many well-documented cases of professional male athletes “behaving badly” and trying to rely on institutional status and various versions of the sporting bubble for shelter (Flood and Dyson; Reel and Crouch; Wade). In the age of mobile and social media, it is increasingly difficult to keep misbehaviour in-house, resulting in a slew of media stories about, for example, drunkenness and sexual misconduct, such as when then-Sydney Roosters co-captain Mitchell Pearce was suspended and fined in 2016 after being filmed trying to force an unwanted kiss on a woman and then simulating a lewd act with her dog while drunk. There is contestation between those who condemn such behaviour as aberrant and those who regard it as the conventional expression of youthful masculinity as part of the familiar “boys will be boys” dictum. The latter naturalise an inequitable gender order, frequently treating sportsmen as victims of predatory women, and ignoring asymmetries of power between men and women, especially in homosocial environments (Toffoletti). For those in the sporting bubble (predominantly elite sportsmen and highly paid executives, also mostly men, with an array of service staff of both sexes moving in and out of it), life is reflected for those being protected via an array of screens (small screens in homes and indoor places of entertainment, and even smaller screens on theirs and others’ phones, as well as huge screens at sport events). These male sport stars are paid handsomely to use their skill and strength to perform for the sporting codes, their every facial expression and bodily action watched by the media and relayed to audiences. This is often a precarious existence, the usually brief career of an athlete worker being dependent on health, luck, age, successful competition with rivals, networks, and club and coach preferences. There is a large, aspirational reserve army of athletes vying to play at the elite level, despite risks of injury and invasive, life-changing medical interventions. Responsibility for avoiding performance and image enhancing drugs (PIEDs) also weighs heavily on their shoulders (Connor). Professional sportspeople, in their more reflective moments, know that their time in the limelight will soon be up, meaning that getting a ticket to the sporting bubble, even for a short time, can make all the difference to their post-sport lives and those of their families. The most vulnerable of the small minority of participants in sport who make a good, short-term living from it are those for whom, in the absence of quality education and prior social status, it is their sole likely means of upward social mobility (Spaaij). Elite sport performers are surrounded by minders, doctors, fitness instructors, therapists, coaches, advisors and other service personnel, all supporting athletes to stay focussed on and maximise performance quality to satisfy co-present crowds, broadcasters, sponsors, sports bodies and mass media audiences. The shield offered by the sporting bubble supports the teleological win-at-all-costs mentality of professional sport. The stakes are high, with athlete and executive salaries, sponsorships and broadcasting deals entangled in a complex web of investments in keeping the “talent” pivotal to the “attention economy” (Davenport and Beck)—the players that provide the content for sale—in top form. Yet, the bubble cannot be entirely secured and poor behaviour or performance can have devastating effects, including permanent injury or disability, mental illness and loss of reputation (Rowe, “Scandals and Sport”). Given this fragile materiality of the sporting bubble, it is striking that, in response to the sudden shutdown following the economic and health crisis caused by the 2020 global pandemic, the leaders of professional sport decided to create more of them and seek to seal the metaphorical and material space with unprecedented efficiency. The outcome was a multi-sided tale of mobility, confinement, capital, labour, and the gendering of sport and society. The Covid-19 Gilded Cage Sociologists such as Zygmunt Bauman and John Urry have analysed the socio-politics of mobilities, whereby some people in the world, such as tourists, can traverse the globe at their leisure, while others remain fixed in geographical space because they lack the means to be mobile or, in contrast, are involuntarily displaced by war, so-called “ethnic cleansing”, famine, poverty or environmental degradation. The Covid-19 global pandemic re-framed these matters of mobilities (Rowe, “Subjecting Pandemic Sport”), with conventional moving around—between houses, businesses, cities, regions and countries—suddenly subjected to the imperative to be static and, in perniciously unreflective technocratic discourse, “socially distanced” (when what was actually meant was to be “physically distanced”). The late-twentieth century analysis of the “risk society” by Ulrich Beck, in which the mysterious consequences of humans’ predation on their environment are visited upon them with terrifying force, was dramatically realised with the coming of Covid-19. In another iteration of the metaphor, it burst the bubble of twenty-first century global sport. What we today call sport was formed through the process of sportisation (Maguire), whereby hyper-local, folk physical play was reconfigured as multi-spatial industrialised sport in modernity, becoming increasingly reliant on individual athletes and teams travelling across the landscape and well over the horizon. Co-present crowds were, in turn, overshadowed in the sport economy when sport events were taken to much larger, dispersed audiences via the media, especially in broadcast mode (Nicholson, Kerr, and Sherwood). This lucrative mediation of professional sport, though, came with an unforgiving obligation to generate an uninterrupted supply of spectacular live sport content. The pandemic closed down most sports events and those that did take place lacked the crucial participation of the co-present crowd to provide the requisite event atmosphere demanded by those viewers accustomed to a sense of occasion. Instead, they received a strange spectacle of sport performers operating in empty “cathedrals”, often with a “faked” crowd presence. The mediated sport spectacle under the pandemic involved cardboard cut-out and sex doll spectators, Zoom images of fans on large screens, and sampled sounds of the crowd recycled from sport video games. Confected co-presence produced simulacra of the “real” as Baudrillardian visions came to life. The sporting bubble had become even more remote. For elite sportspeople routinely isolated from the “common people”, the live sport encounter offered some sensory experience of the social – the sounds, sights and even smells of the crowd. Now the sporting bubble closed in on an already insulated and insular existence. It exposed the irony of the bubble as a sign of both privileged mobility and incarcerated athlete work, both refuge and prison. Its logic of contagion also turned a structure intended to protect those inside from those outside into, as already observed, a mechanism to manage the threat of insiders to outsiders. In Australia, as in many other countries, the populace was enjoined by governments and health authorities to help prevent the spread of Covid-19 through isolation and immobility. There were various exceptions, principally those classified as essential workers, a heterogeneous cohort ranging from supermarket shelf stackers to pharmacists. People in the cultural, leisure and sports industries, including musicians, actors, and athletes, were not counted among this crucial labour force. Indeed, the performing arts (including dance, theatre and music) were put on ice with quite devastating effects on the livelihoods and wellbeing of those involved. So, with all major sports shut down (the exception being horse racing, which received the benefit both of government subsidies and expanding online gambling revenue), sport organisations began to represent themselves as essential services that could help sustain collective mental and even spiritual wellbeing. This case was made most aggressively by Australian Rugby League Commission Chairman, Peter V’landys, in contending that “an Australia without rugby league is not Australia”. In similar vein, prominent sport and media figure Phil Gould insisted, when describing rugby league fans in Western Sydney’s Penrith, “they’re lost, because the football’s not on … . It holds their families together. People don’t understand that … . Their life begins in the second week of March, and it ends in October”. Despite misgivings about public safety and equality before the pandemic regime, sporting bubbles were allowed to form, re-form and circulate. The indefinite shutdown of the National Rugby League (NRL) on 23 March 2020 was followed after negotiation between multiple entities by its reopening on 28 May 2020. The competition included a team from another nation-state (the Warriors from Aotearoa/New Zealand) in creating an international sporting bubble on the Central Coast of New South Wales, separating them from their families and friends across the Tasman Sea. Appeals to the mental health of fans and the importance of the NRL to myths of “Australianness” notwithstanding, the league had not prudently maintained a financial reserve and so could not afford to shut down for long. Significant gambling revenue for leagues like the NRL and Australian Football League (AFL) also influenced the push to return to sport business as usual. Sport contests were needed in order to exploit the gambling opportunities – especially online and mobile – stimulated by home “confinement”. During the coronavirus lockdowns, Australians’ weekly spending on gambling went up by 142 per cent, and the NRL earned significantly more than usual from gambling revenue—potentially $10 million above forecasts for 2020. Despite the clear financial imperative at play, including heavy reliance on gambling, sporting bubble-making involved special licence. The state of Queensland, which had pursued a hard-line approach by closing its borders for most of those wishing to cross them for biographical landmark events like family funerals and even for medical treatment in border communities, became “the nation's sporting hub”. Queensland became the home of most teams of the men’s AFL (notably the women’s AFLW season having been cancelled) following a large Covid-19 second wave in Melbourne. The women’s National Netball League was based exclusively in Queensland. This state, which for the first time hosted the AFL Grand Final, deployed sport as a tool in both national sports tourism marketing and internal pre-election politics, sponsoring a documentary, The Sporting Bubble 2020, via its Tourism and Events arm. While Queensland became the larger bubble incorporating many other sporting bubbles, both the AFL and the NRL had versions of the “fly in, fly out” labour rhythms conventionally associated with the mining industry in remote and regional areas. In this instance, though, the bubble experience did not involve long stays in miners’ camps or even the one-night hotel stopovers familiar to the popular music and sport industries. Here, the bubble moved, usually by plane, to fulfil the requirements of a live sport “gig”, whereupon it was immediately returned to its more solid bubble hub or to domestic self-isolation. In the space created between disciplined expectation and deplored non-compliance, the sporting bubble inevitably became the scrutinised object and subject of scandal. Sporting Bubble Scandals While people with a very low risk of spreading Covid-19 (coming from areas with no active cases) were denied entry to Queensland for even the most serious of reasons (for example, the death of a child), images of AFL players and their families socialising and enjoying swimming at the Royal Pines Resort sporting bubble crossed our screens. Yet, despite their (players’, officials’ and families’) relative privilege and freedom of movement under the AFL Covid-Safe Plan, some players and others inside the bubble were involved in “scandals”. Most notable was the case of a drunken brawl outside a Gold Coast strip club which led to two Richmond players being “banished”, suspended for 10 matches, and the club fined $100,000. But it was not only players who breached Covid-19 bubble protocols: Collingwood coaches Nathan Buckley and Brenton Sanderson paid the $50,000 fine imposed on the club for playing tennis in Perth outside their bubble, while Richmond was fined $45,000 after Brooke Cotchin, wife of team captain Trent, posted an image to Instagram of a Gold Coast day spa that she had visited outside the “hub” (the institutionally preferred term for bubble). She was subsequently distressed after being trolled. Also of concern was the lack of physical distancing, and the range of people allowed into the sporting bubble, including babysitters, grandparents, and swimming coaches (for children). There were other cases of players being caught leaving the bubble to attend parties and sharing videos of their “antics” on social media. Biosecurity breaches of bubbles by players occurred relatively frequently, with stern words from both the AFL and NRL leaders (and their clubs) and fines accumulating in the thousands of dollars. Some people were also caught sneaking into bubbles, with Lekahni Pearce, the girlfriend of Swans player Elijah Taylor, stating that it was easy in Perth, “no security, I didn’t see a security guard” (in Barron, Stevens, and Zaczek) (a month later, outside the bubble, they had broken up and he pled guilty to unlawfully assaulting her; Ramsey). Flouting the rules, despite stern threats from government, did not lead to any bubble being popped. The sport-media machine powering sporting bubbles continued to run, the attendant emotional or health risks accepted in the name of national cultural therapy, while sponsorship, advertising and gambling revenue continued to accumulate mostly for the benefit of men. Gendering Sporting Bubbles Designed as biosecurity structures to maintain the supply of media-sport content, keep players and other vital cogs of the machine running smoothly, and to exclude Covid-19, sporting bubbles were, in their most advanced form, exclusive luxury camps that illuminated the elevated socio-cultural status of sportsmen. The ongoing inequalities between men’s and women’s sport in Australia and around the world were clearly in evidence, as well as the politics of gender whereby women are obliged to “care” and men are enabled to be “careless” – or at least to manage carefully their “duty of care”. In Australia, the only sport for women that continued during the height of the Covid-19 lockdown was netball, which operated in a bubble that was one of sacrifice rather than privilege. With minimum salaries of only $30,000 – significantly less than the lowest-paid “rookies” in the AFL – and some being mothers of small children and/or with professional jobs juggled alongside their netball careers, these elite sportswomen wanted to continue to play despite the personal inconvenience or cost (Pavlidis). Not one breach of the netballers out of the bubble was reported, indicating that they took their responsibilities with appropriate seriousness and, perhaps, were subjected to less scrutiny than the sportsmen accustomed to attracting front-page headlines. National Netball League (also known after its Queensland-based naming rights sponsor as Suncorp Super Netball) players could be regarded as fortunate to have the opportunity to be in a bubble and to participate in their competition. The NRL Women’s (NRLW) Premiership season was also completed, but only involved four teams subject to fly in, fly out and bubble arrangements, and being played in so-called curtain-raiser games for the NRL. As noted earlier, the AFLW season was truncated, despite all the prior training and sacrifice required of its players. Similarly, because of their resource advantages, the UK men’s and boy’s top six tiers of association football were allowed to continue during lockdown, compared to only two for women and girls. In the United States, inequalities between men’s and women’s sports were clearly demonstrated by the conditions afforded to those elite sportswomen inside the Women’s National Basketball Association (WNBA) sport bubble in the IMG Academy in Florida. Players shared photos of rodent traps in their rooms, insect traps under their mattresses, inedible food and blocked plumbing in their bubble accommodation. These conditions were a far cry from the luxury usually afforded elite sportsmen, including in Florida’s Walt Disney World for the men’s NBA, and is just one of the many instances of how gendered inequality was both reproduced and exacerbated by Covid-19. Bursting the Bubble As we have seen, governments and corporate leaders in sport were able to create material and metaphorical bubbles during the Covid-19 lockdown in order to transmit stadium sport contests into home spaces. The rationale was the importance of sport to national identity, belonging and the routines and rhythms of life. But for whom? Many women, who still carry the major responsibilities of “care”, found that Covid-19 intensified the affective relations and gendered inequities of “home” as a leisure site (Fullagar and Pavlidis). Rates of domestic violence surged, and many women experienced significant anxiety and depression related to the stress of home confinement and home schooling. During the pandemic, women were also more likely to experience the stress and trauma of being first responders, witnessing virus-related sickness and death as the majority of nurses and care workers. They also bore the brunt of much of the economic and employment loss during this time. Also, as noted above, livelihoods in the arts and cultural sector did not receive the benefits of the “bubble”, despite having a comparable claim to sport in contributing significantly to societal wellbeing. This sector’s workforce is substantially female, although men dominate its senior roles. Despite these inequalities, after the late March to May hiatus, many elite male sportsmen – and some sportswomen - operated in a bubble. Moving in and out of them was not easy. Life inside could be mentally stressful (especially in long stays of up to 150 days in sports like cricket), and tabloid and social media troll punishment awaited those who were caught going “over the fence”. But, life in the sporting bubble was generally preferable to the daily realities of those afflicted by the trauma arising from forced home confinement, and for whom watching moving sports images was scant compensation for compulsory immobility. The ethical foundation of the sparkly, ephemeral fantasy of the sporting bubble is questionable when it is placed in the service of a voracious “media sports cultural complex” (Rowe, Global Media Sport) that consumes sport labour power and rolls back progress in gender relations as a default response to a global pandemic. Covid-19 dramatically highlighted social inequalities in many areas of life, including medical care, work, and sport. For the small minority of people involved in sport who are elite professionals, the only thing worse than being in a sporting bubble during the pandemic was not being in one, as being outside precluded their participation. Being inside the bubble was a privilege, albeit a dubious one. But, as in wider society, not all sporting bubbles are created equal. Some are more opulent than others, and the experiences of the supporting and the supported can be very different. The surface of the sporting bubble may be impermanent, but when its interior is opened up to scrutiny, it reveals some very durable structures of inequality. Bubbles are made to burst. They are, by nature, temporary, translucent structures created as spectacles. As a form of luminosity, bubbles “allow a thing or object to exist only as a flash, sparkle or shimmer” (Deleuze, 52). In echoing Deleuze, Angela McRobbie (54) argues that luminosity “softens and disguises the regulative dynamics of neoliberal society”. The sporting bubble was designed to discharge that function for those millions rendered immobile by home confinement legislation in Australia and around the world, who were having to deal with the associated trauma, risk and disadvantage. 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[Truncated abstract] Chapter 1 provides an introduction to the 'sarcophagine' class of ligands and the field of metallopolymers. The synthesis, stereochemistry, physical properties and functionalisation of 'sarcophagines' and their metal complexes are discussed. A brief overview of the burgeoning field of metallopolymers is given with specific mention of the synthetic routes to pendant metallopolymers, and how these could be employed to prepared cage amine containing metallopolymers. Chapter 2 deals with the synthesis, characterisation and reactivity of cinnamylamino and styrylamido derivatives of the cage amines [Co((NH2)2sar)]3+, [Co((CH3)(NH2)sar)]3+ and [Cu((NH2)2sar)]2+. The cinnamylamino derivatives were prepared using reductive alkylation of the aforementioned amines with cinnamaldehyde. Procedures were developed to isolate the complexes without causing unwanted additions to the double bond. The cinnamylamino derivatives displayed unexpected reactivity towards a range of reducing agents, resulting in unexpected reduction of the double bond and cleavage of the cinnamyl group, but ultimately in the preparation of phenylpropylamino derivatives of [Co((NH2)2sar)]3+ and [Co((CH3)(NH2)sar)]3+. Attempts to rationalise the reactivity of the double bond have been explored based upon the physical properties and reactivity of the double bond. The styrylamido derivatives were prepared by treatment of the cage amines with 4-vinylbenzoyl chloride, and the complexes isolated in a similar manner to those of the cinnamylamino derivatives to ensure the amide linkage remained intact. Most of the complexes have been structurally characterised. ... Both the 2-thienyl and 3-thienyl derivatives of [Co((NH2)2sar)]3+ and [Co((CH3)(NH2)sar)]3+ have been prepared using reductive alkylation with the respective carboxaldehydes of thiophene. One of the optically pure isomers has been prepared. The complexes have been fully characterised including structural characterisation. Polymerisation of the thiophene-cage amine complexes was investigated under a range of chemical and electrochemical conditions, though polymerisation was never observed. Cleavage of the thienyl groups was observed when ceric ammonium nitrate in nitric acid was used as the oxidant. The attachment of oligothiophenes and mixed pyrrole-thiophene oligomers to cage amines were investigated using reductive alkylation and various pyrrole ring-forming reactions about the apical amino groups, though none of the desired complexes were isolated, reasons for the lack of reactivity were discussed. An efficient synthesis of N-(4-benzoic acid)- 2,5-di(2-thienyl)pyrrole was developed and was shown to the electropolymerisable, albeit the polymer films were non-conducting. Attempts to couple N-(4-benzoic acid)- 2,5-di(2-thienyl)pyrrole with a cage amine via its acid chloride were complicated by decomposition reactions, the nature of one of these products is discussed. Chapter 5 presents investigations into the preparation of simple complexes containing multiple cage amines using alkylation and acylation procedures with aromatic substrates. The complexes were found to exhibit some interesting electrochemical and chemical properties, demonstrating that even simple multiple cage amine species can display complicated and interesting behaviour.

Abstract This study presents the design and development of a compliant multi-link hopping mechanism actuated by a single DC motor. Two main design goals are to have a single piece designed main body for the jumping robot and a passive stabilizer to allow consecutive jumps. Mechanism consists of monolithically designed large deflecting main body incorporating the gears and initially curved flexure hinge. Due to the limitations of the design goal, revolute motion between top and bottom legs on the main body are realized by a compliant link which replaces the need of ball bearings. Also, continuous energy store and release during jumping is ensured by the same flexure hinges. Passive self-righting cage is attached to the bottom of the main body to maintain upright position both in landing and takeoff. The cage allows the center of mass to stay in the vertical plane to prevent tilting. During landing, cage absorbs the impact and allows the main body to roll to its initial configuration so that the robot can complete jumping. Mechanism parts including the cage are 3D printed using PETG. Design optimization of the body parts including the rigid legs and flexure hinges are analyzed both experimentally and analytically. Finite element analysis is performed to calculate the equivalent stiffness and natural frequency of the jumping robot and simplified mathematical model is derived using rigid body dynamics.

Cavitation is a harmful phenomenon for control valves. Starting from noise and vibration, cavitation can bring erosion and pitting of mechanical parts. Experimental costs for cavitation tests are high, not even considering the difficulties to test large-sized valves. For those reasons a CFD analysis could be an attractive solution to predict cavitation. However, a reliable numerical prediction of cavitation inception is hard to achieve and the computational cost of complex multi-phase models, necessary for a correct description of this phenomenon, is often very high. The purpose of this research is to overcome those difficulties by using a single-phase model to predict the onset of cavitation, in terms of the incipient cavitation index introduced in several technical standards. A method, based on the generalized pressure criterion reported in previous works, is applied to particularly complex control devices, namely the Cage Ball control valves, in which perforated plates are inserted to increase the energy dissipation with respect to a traditional Ball valve. Numerical results are compared with our own experimental data of acceleration induced by cavitation vibrations, showing good agreement. The final result is a simple and reliable method, with low computational cost, to evaluate the incipient cavitation index for control valves.