Radical Self Research Articles

Computational Investigation of Substituent Effects on the Alcohol + Carbonyl Channel of Peroxy Radical Self- and Cross-Reactions

Organic peroxy radicals (RO2) are key intermediates in atmospheric chemistry and can undergo a large variety of both uni- and bimolecular reactions. One of the least understood reaction classes of RO2 are their self- and cross-reactions: RO2 + R'O2. In our previous work, we have investigated how RO2 + R'O2 reactions can lead to the formation of ROOR' accretion products through intersystem crossings and subsequent recombination of a triplet intermediate complex 3(RO···OR'). Accretion products can potentially have very low saturation vapor pressures, and may therefore participate in the formation of aerosol particles. In this work, we investigate the competing H-shift channel, which leads to the formation of more volatile carbonyl and alcohol products. This is one of the main, and sometimes the dominant, RO2 + R'O2 reaction channels for small RO2. We investigate how substituents (R and R' groups) affect the H-shift barriers and rates for a set of 3(RO···OR') complexes. The variation in barrier heights and rates is found to be surprisingly small, and most computed H-shift rates are fast: around 108-109 s-1. We find that the barrier height is affected by three competing factors: (1) the weakening of the breaking C-H bond due to interactions with adjacent functional groups; (2) the overall binding energy of the 3(RO···OR'), which tends to increase the barrier height; and (3) the thermodynamic stability of the reaction products. We also calculated intersystem crossing rate coefficients (ISC) for the same systems and found that most of them were of the same order of magnitude as the H-shift rates. This suggests that both studied channels are competitive for small and medium-sized RO2. However, for complex enough R or R' groups, the binding energy effect may render the H-shift channel uncompetitive with intersystem crossings (and thus ROOR' formation), as the rate of the latter, while variable, seems to be largely independent of system size. This may help explain the experimental observation that accretion product formation becomes highly effective for large and multifunctional RO2.

Holy Water.

Holy Water explores the infiltration of colonization on my home island, Belau, and the impact that it has had on our relationships to each other, our health, and our indigenous ways of knowing and being. I intentionally use baptism and Western Christianity as a metaphor for colonization to highlight the effect White supremacy has had on my people, while also challenging the ways in which we take part in continuing our colonial reality. I often run into contradictions about what Western culture deems we should be and who we actually are as Palauans-birthing this story of struggle into reclamation. This piece continually addresses the subject "unko," to highlight the tensions between myself, a queer femme diasporic micronesian, and the elder men in my community who have been forced into Westernization, and therefore enforce those same values and societal norms on my expression of self. I believe in radical self love and community care. I honor my ancestors and their fight for our liberation, and carry their legacy into my own journey. The health of my community depends on our ability to think critically about where we've been, who we are, and where we want to be. Holy Water is a testament to the reclamation of our stories, our history, and our collective power. To view the original version of this poem, see the supplemental material section of this article online.

Dancing Toward Freedom

Dancing Toward Freedom

Comparing Reaction Routes for 3(RO···OR') Intermediates Formed in Peroxy Radical Self- and Cross-Reactions.

Organic peroxy radicals (RO2) are key intermediates in the chemistry of the atmosphere. One of the main sink reactions of RO2 is the recombination reaction RO2 + R'O2, which has three main channels (all with O2 as a coproduct): (1) R-H═O + R'OH, (2) RO + R'O, and (3) ROOR'. The RO + R'O "alkoxy" channel promotes radical and oxidant recycling, while the ROOR' "dimer" channel leads to low-volatility products relevant to aerosol processes. The ROOR' channel has only recently been discovered to play a role in the gas phase. Recent computational studies indicate that all of these channels first go through an intermediate complex 1(RO···3O2···OR'). Here, 3O2 is very weakly bound and will likely evaporate from the system, giving a triplet cluster of two alkoxy radicals: 3(RO···OR'). In this study, we systematically investigate the three reaction channels for an atmospherically representative set of RO + R'O radicals formed in the corresponding RO2 + R'O2 reaction. First, we systematically sample the possible conformations of the RO···OR' clusters on the triplet potential energy surface. Next, we compute energetic parameters and attempt to estimate reaction rate coefficients for the three channels: evaporation/dissociation to RO + R'O, a hydrogen shift leading to the formation of R'-H═O + ROH, and "spin-flip" (intersystem crossing) leading to, or at least allowing, the formation of ROOR' dimers. While large uncertainties in the computed energetics prevent a quantitative comparison of reaction rates, all three channels were found to be very fast (with typical rates greater than 106 s-1). This qualitatively demonstrates that the computationally proposed novel RO2 + R'O2 reaction mechanism is compatible with experimental data showing non-negligible branching ratios for all three channels, at least for sufficiently complex RO2.

"Comparing Reaction Routes for 3(RO…OR') Intermediates Formed in Peroxy Radical Self- and Cross-Reactions."

"Comparing Reaction Routes for 3(RO…OR') Intermediates Formed in Peroxy Radical Self- and Cross-Reactions."

Bibler's case

In 2018, the 100th anniversary of the birth of Vladimir Solomonovich Bibler (1918-2000) was celebrated. This date is celebrated in Russia (see, for example, publications in "Voprosy filosofii"), and in Ukraine, in Kiev, where gathered disciples, followers, listeners Bibler from different ends of the earth and where, in addition to the roundtable, presentation of the book by Bibler in the Ukrainian language (see the website "Bibler and around"). The materials of the round table held at the Institute of philosophy of the Russian Academy of Sciences were published in the online magazine Vox, whose employees care not only about Bibler's philosophical legacy, but also about His life, because his biography is, as one of Bibler's students P. D. Tishchenko said at the round table, "the experience of radical self — choice".

Narrating Political Imprisonment in Tsarist Russia: Bakunin, Goethe, Hegel

How have modern cultures of dissent learnt to narrate the experience of political imprisonment? From 1851 to 1853, M. A. Bakunin was incarcerated in St Petersburg's Peter and Paul Fortress. Here, the “father of Russian anarchism” wrote what has become known as hisConfession: an account of his personal and political development, penned in the most notorious prison of the Russian autocracy at the behest of the tsar. Previous scholarship has focused entirely on the content of this peculiar text. The present article is the first to mobilize extensive archival research—on its carceral conditions of production and intellectual conditions of possibility—in order to understand the form of Bakunin'sConfession. Doing so reveals the text as one of the first RussianBildungsromane: the birth of a genre whereby the imprisoned self became legible through a new epistemology of self and history between Goethe and Hegel. Excavating the nature and afterlives of this novel political aesthetics provides original insights into the “politicization” of state incarceration in European history, the origins of modern Russian autobiographics, and the construction of the radical self.

In Her Own Voice: Charmayne D'Souza

The present paper aims to study Charmayne D'Souza's one and only volume of poetry, A Spelling Guide to Woman. Her poetry shows texture of western feminism where she expresses the radical self of a reformist kind with the strong belief of an iconoclast. Poetry is a two-way process for D'Souza. She uses poetry for not only verbalizing 'personal as political' but also for making the public as personal and as a medium to resist codification of patriarchal discourses. Simone de Beauvoir in The Second Sex has stated that each consciousness defines itself as subject by defining the other consciousness as object. A woman is a paragon of oppressed consciousness, an object in the male psyche. Patriarchy controls the lives of women. Germaine Greer, in this context, has said that patriarchy makes women eunuch. It castrates women making them deprived of subjection and treat them as a mere object.

First oxidation products from the reaction of hydroxyl radicals with isoprene for pristine environmental conditions

Isoprene, C5H8, inserts about half of the non-methane carbon flux of biogenic origin into the atmosphere. Its degradation is primarily initiated by the reaction with hydroxyl radicals. Here we show experimentally the formation of reactive intermediates and corresponding closed-shell products from the reaction of hydroxyl radicals with isoprene for low nitric oxide and low hydroperoxy radical conditions. Detailed product analysis is achieved by mass spectrometric techniques. Quantum chemical calculations support the usefulness of applied ionization schemes. Observed peroxy radicals are the isomeric HO-C5H8O2 radicals and their isomerization products HO-C5H8(O2)O2, bearing most likely an additional hydroperoxy group, and in traces HO-C5H8(O2)2O2 with two hydroperoxy groups. Main closed-shell products from unimolecular peroxy radical reactions are hydroperoxy aldehydes, C5H8O3, and smaller yield products with the composition C5H8O4 and C4H8O5. Detected signals of C10H18O4, C10H18O6, and C5H10O2 stand for products arising from peroxy radical self- and cross-reactions.

Radical Theatrics: Put-ons, Politics and the Sixties by Craig J. Peariso

Reviewed by: Radical Theatrics: Put-ons, Politics and the Sixties by Craig J. Peariso Alan Filewod Craig J. Peariso, Radical Theatrics: Put-ons, Politics and the Sixties (Seattle: University of Washington Press 2014) At the time I write this review, Donald Trump is bellowing his way along the campaign trail and edging closer to the presidency. As his campaign gained momentum over the fall, media pundits who had courted him – and fed his craving for publicity – publicly wondered if he was in fact serious. Speculations that the campaign was a stunt, that he was using it to inflate his "brand," and that he would stage a last-minute exit, were fueled by the apparent delight he took in his extremist and reckless antics. But as the election nears, he shows no sign of anything except a lust for power. If he was a joke at first, he has manipulated the media brilliantly to put the joke back on them. Paradoxically, as his self-performance becomes more erratic and bellicose, the media falls in line to accept him as a legitimate and credible candidate. Is it because the media attention span is always fixed on the present moment and the latest soundbite, or is it because, even at its craziest, the performance of the radical self is functionally a legitimizing tactic? No matter what he does, Trump becomes more "real." The mediatized performance of extremism in the cause of politics may be as old as mass media, and adaptive across its various forms, but as Craig Peariso argues persuasively, something changed in the 1960s when radical protest elevated the "put-on" (a phrase he borrows from [End Page 294] Jacob Brackman) into a political tactic. For Peariso, as an art historian, the radical theatrics of the Yippies, the Gay Liberation Front, and the Black Panthers (the three instantiations that form his case studies) can be understood as performances of the put-on through which we can read the limits and paradoxes of the political realities they disturb. The core problem, which he traces through the theories that work through the historical case studies (beginning with Herbert Marcuse and Susan Sontag), is that radical performance is necessarily subject to assimilation; performance becomes a commodity, and performances that strive to disrupt the system of signification and commodification ultimately falter; they appear to "fail" because they cannot disrupt their own representation. Looking at Abbie Hoffman's self-performance as the trickster of the revolution, Peariso sees something more than the buffoonery that distressed the radical left. Hoffman, he suggests, embodied a sophisticated critique of the limits of radical action in the mediatized postmodern. Similarly, Peariso examines Eldridge Cleaver's hyper-sexualized self-staging as a put-on that replayed and reflected pervasive social anxiety about Black masculinity. In both cases, the "performers" were authors and captives of their performances. His other case study, dealing with the crisis in the New York queer community and the emergence of the Gay Activists Alliance (gaa), questions whether the confrontational tactics of camp and drag constituted a sophisticated political critique of the ways in which the dominant culture absorbs and constrains all forms of expression. Peariso's analyses are grounded in a richly detailed art-historical materiality; in each of these case studies he situates the social performance in the contexts of its contemporary theory, effectively plumbing the relationship between radical action and discourse to argue that theatricality can be both political resistance and critique. Despite the title, this study is less about theatrics than it is about the historical moment of emergence of "new, more self-conscious and aesthetically complex forms of political resistance." (163) For Peariso, the put-on may mark the failure of signification, but he affirms the necessity of what he calls aestheticized resistance while pointing to the recurring dilemma of actions that attempt "to articulate dissent while brushing against the limits of historical possibility." (185) The idea of failure provides the ground for his afterword, which addresses the contemporary dilemma of the put-on. Looking specifically at the Yes Men, who famously try to expose corporate crimes through provocative straight-faced but parodic interventions, he asks why their targets so often appear...

Islomania, Dilettantism, and the Devolutionary Vision of Lawrence’s The Man Who Loved Islands

<p>This study investigates how science (i.e., Darwinian perspectives) and myth inform the discourse and structure of D.H. Lawrence’s <em>The Man Who Loved Islands</em>. The study posits that the novella harbors a dialectical view of devolution in the context of the detrimental biocultual and cognitive implications of the modern cults of dilettantism and dandyism. Following an integrative approach that conjoins the archetypal, the cultural, and Darwinian perspectives, the study argues that, in terms of technique, Lawrence’s satirical novella employs what Lawrence Durrell termed “islomania” (obsession with islands) to foreground dilettantism as a flawed vision that sidesteps anthropocentricity as well as biocentricity. Moreover, it employs the master image of the desexualized bourgeois dilettante self that takes on the archetypal guise of anti-Eros to conceptualize the idea of devolution, or rather the devolutionary. Another technique that the novella engages is a disinterested authorial tone. Like in scientific discourse, the text is projected as illustrative of a fundamental, universal law or axiom that can harbor an empirical gist: what detrimental pathologies certain general contingencies and cultural practices may effect? In short, as a mock utopia, Lawrence's novella is about the insurvivability of the radical self that succeeds in demonizing heterogeneity and language.</p><p><strong><em>Keywords</em></strong><em>: </em>D.H. Lawrence, Darwinism in literature, Dilettantism, Dandyism, Biology in literature, Islands in literature</p>

Reassessing the photochemical production of methanol from peroxy radical self and cross reactions using the STOCHEM-CRI global chemistry and transport model

Methanol (CH3OH) is an oxygenated volatile organic compound (VOC) and one of the most abundant species present in the troposphere. The mass of CH3OH in the atmospheric reservoir, its annual mass flux from sources to sinks, and its global budget have been investigated using STOCHEM-CRI, a global three-dimensional chemistry transport model. Our study shows that the global burden of methanol is 5 Tg. The atmospheric life-time of CH3OH is found to be 6.1 days which falls within the range of previous modelling studies. The impact of peroxy radicals on the photochemical production of CH3OH has been studied and suggests that NMVOCs (non-methane Volatile Organic Compounds) are an important source of both peroxy radicals and CH3OH. The photochemical production routes of CH3OH are found to be 48 Tg/yr, which are higher than the previous studies and contributes significantly to the total global methanol sources of 287 Tg/yr. An additional CH3OH production of 8.2 Tg/yr from the reaction of methyl peroxy radicals (CH3O2) with hydroxyl radicals (OH) could be a significant additional source of CH3OH particularly over the tropical oceans which would lead to a revision of the global sources and life cycle of CH3OH.

Vulnerability and the Sovereign Individual: Nussbaum and Nietzsche on the role of agency and vulnerability in personhood

In her paper Pity and Mercy: Nietzsche's Stoicism, Martha Nussbaum argues that Nietzsche's philosophical project can be seen in part as an attempt to ‘bring about a revival of Stoic values of self-command and self-transformation’. She argues that, to his detriment, Nietzsche's ‘Sovereign Individual’ epitomises a kind of stoic ideal of inner strength and self-sufficiency that ‘goes beyond Stoicism’ in its valorisation of radical self emancipation from the contingencies of life and from our own human vulnerability. Nussbaum thus urges us to question whether the picture of strength in Nietzsche's Sovereign Individual is really a picture of human strength at which we would be willing to, or at which we ought to, aim. In this paper I take up Nussbaum's challenge, arguing that Nietzsche's Sovereign Individual is both less stoical and provides us with a far more attractive picture of personhood than Nussbaum suggests.

Coupling of HO<sub>x</sub>, NO<sub>x</sub> and halogen chemistry in the antarctic boundary layer

Abstract. A modelling study of radical chemistry in the coastal Antarctic boundary layer, based upon observations performed in the course of the CHABLIS (Chemistry of the Antarctic Boundary Layer and the Interface with Snow) campaign at Halley Research Station in coastal Antarctica during the austral summer 2004/2005, is described: a detailed zero-dimensional photochemical box model was used, employing inorganic and organic reaction schemes drawn from the Master Chemical Mechanism, with additional halogen (iodine and bromine) reactions added. The model was constrained to observations of long-lived chemical species, measured photolysis frequencies and meteorological parameters, and the simulated levels of HOx, NOx and XO compared with those observed. The model was able to replicate the mean levels and diurnal variation in the halogen oxides IO and BrO, and to reproduce NOx levels and speciation very well. The NOx source term implemented compared well with that directly measured in the course of the CHABLIS experiments. The model systematically overestimated OH and HO2 levels, likely a consequence of the combined effects of (a) estimated physical parameters and (b) uncertainties within the halogen, particularly iodine, chemical scheme. The principal sources of HOx radicals were the photolysis and bromine-initiated oxidation of HCHO, together with O(1D) + H2O. The main sinks for HOx were peroxy radical self- and cross-reactions, with the sum of all halogen-mediated HOx loss processes accounting for 40% of the total sink. Reactions with the halogen monoxides dominated CH3O2-HO2-OH interconversion, with associated local chemical ozone destruction in place of the ozone production which is associated with radical cycling driven by the analogous NO reactions. The analysis highlights the need for observations of physical parameters such as aerosol surface area and boundary layer structure to constrain such calculations, and the dependence of simulated radical levels and ozone loss rates upon a number of uncertain kinetic and photochemical parameters for iodine species.

Nitroxyl radical self assembled monolayers: Ion pairing investigation in organic and aqueous media

Self assembled monolayers (SAMs) formed from TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) derivative thiols have been studied by electrochemical quartz crystal microbalance (EQCM) in both aqueous and non-aqueous solvents. The in situ study of the mass transport occurring during the oxidation of TEMPO provides evidence of a ion pair formation without incorporation of solvent in densely packed nitroxyl radical SAMs. For SAMs having a low nitroxyl radical surface coverage, the effect of mixed SAMs is evidenced and seems to avoid the solvent incorporation.

Risks and pleasures: a Deleuzo‐Guattarian pedagogy of desire in education

This article provides an analysis of a pedagogy of desire from a Deleuzo‐Guattarian perspective. A pedagogy of desire can be theorised in ways that mobilise creative, transgressive and pleasurable forces within teaching and learning environments. It also enables a new view on affect in education as a landscape of becoming in which forces, surfaces and flows of teachers/students are caught up in a desiring ontology. This marks an attempt to reclaim the notion of desire away from a purely negative, repressive or libidinal framework. The claim of pedagogy of desire is that through the mobilisation and release of desiring production, teachers and students make available to themselves the powerful flows of desire, thereby turning themselves into subjects who subvert normalised representations and significations and find access to a radical self. Some strategies and practical implications are offered to suggest how this approach to pedagogy may function in educational contexts.

On the relationship of HO2 + RO2 with j(O1D) during the Free Tropospheric Experiment (FREETEX '96) at the Jungfraujoch Observatory(3580 m above sea level) in the Swiss Alps

Continuous measurements of peroxy radicals (HO2+RO2), the photolysis rate coefficients j(NO2) and j(O1D), and a number of other trace gases including O3, NOx, and CO, were carried out at the alpine site at Jungfraujoch (3580 m asl), Switzerland, in April/May 1996 during the Free Tropospheric Experiment (FREETEX '96). In spring, the Jungfraujoch Observatory is very often located in the lower free troposphere. A mean midday concentration of 17.1±2.2 parts per trillion by volume (pptv) was calculated from continuous measurements of the sum of inorganic and organic peroxy radicals using the chemical amplification technique. The average diurnal cycles for peroxy radicals and the photolysis rate coefficient j)O1D) during FREETEX '96 showed a statistically more significant square root than first‐order relationship, indicative of a relatively clean atmosphere at the mountain site, where peroxy radical self‐ and cross‐reactions were the dominant peroxy radical loss processes. The average ozone diurnal cycle during FREETEX '96 displayed an increase of about 2 ppbv during the daytime despite the square root relationship. Similar results were derived from individual days during the campaign. A simple photochemical box model indicated that there is a regime in NO concentration from about 20 pptv to 100 pptv where a better square root (than first‐order) correlation between peroxy radicals and j(O1D) is accompanied by net ozone production. Taking into account that median daytime concentrations of NO at Jungfraujoch range from 51 pptv in March to 93 pptv in April, it is suggested that Jungfraujoch, during FREETEX '96, has been in the net ozone production regime in spite of the observed square root dependence of peroxy radicals on j(O1D)

Dialectics of the Absolute

My title indicates three central notions: Dialectics, the Absolute, and System. It is the notion of system that indicates the goal of this essay: namely, to bring together these three notions in a systematic coherence in order to elucidate the character of Husserl's late philosophy. Such a task seems to call for a "speculative" and not a phenomenological treatment-at least in the common usage of the term "phenomenological." Moreover, it might seem rather futile to attempt to apply these notions to Husserl's phenomenology. Husserl's reservations towards systematic philosophy are well-known and have often been discussed (and shall not be repeated here). However, there are numerous motives for Husserl's later move towards a decisive "will to a system." One dominant motive is certainly his perceived competition with the Neo-Kantians which led him to attempt to formulate and work out his phenomenological system in his mature years.1 Yet there must also be immanent reasons for this effort-and also for his great distress in failing to achieve what he had set out to do. In his last years, when he realized he wouldn't be able to complete his task, he at least wanted to reflect this systematic scope in his Nachlass in order to leave to his phenomenological successors a useful source of material in the form of manuscripts. The phenomenological movement itself was supposed to carry out and in this process constitute the system of phenomenology as the decisive figure in the history of Western philosophy. As I have indicated, Husserl unsuccessfully attempted several times to work out this system. Moreover, the development of the phenomenological movement (a term coined by Husserl himself) after his death can be interpreted as a refusal to carry out his master plan, insofar as it meant that each phenomenological scientist would have to partake in this endless task. Yet even given these factual obstacles which left the system unfinished, we cannot simply pass over this "will to a system" as seems to be the tendency in a great deal of Husserl scholarship today. To neglect this "systematic Husserl" is to do an injustice to Husserl's innermost intentions. If the will to a system is so apparent-- as is the case in the late Husserl--the duty of an honest interpreter is to at least attempt to understand what Husserl had in mind, even if such an attempt leads to the consequence of having to reject this systematic conception, precisely for the same reasons that guided Husserl's initial formulation of this system. It is one fundamental insight of the late Husserl that phenomenology cannot do without a systematic conception serving as a guiding clue as well as embedding the intricate detailed analyses into a systematic totality. Not taking into consideration the nature of this systematic totality has always already tacitly given an answer to the question of systematics. But, for all that, we need not go as far as Fink did and critically assert that phenomenological analysis without speculation "is not worth a dime: 'z Instead, we need only acknowledge that an implicit understanding of a systematic totality is always presupposed. Yet does not harboring unchecked presuppositions contradict the very principle of phenomenological analysis, i.e., the task of achieving a universal understanding, which can only be reached when we thematize this understanding and which in turn calls for an understanding of this understanding? Therefore we can already say that neglecting to subject the results of phenomenological analysis to an interpretation regarding their meaning and their sense-in other words, their position within a system-disregards the fundamental intention of phenomenological inquiry, namely to practice radical self introspection and self critique and to give an account (the famous logon didonai) for these results. If all data experienced in the lived-experience of transcendental life calls for a critique, this critique in turn calls for a critique. …

The temperature dependence of the rate coefficients for ?-hydroxyperoxy radical self reactions

A laser-flash photolysis/UV absorption technique has been used to study the temperature dependence (from T = 300 - 470 K) of the self-reaction kinetics of representative primary secondary and tertiary β-hydroxyperoxy radicals The following Arrhenius expressions were derived for the rate coefficients of reactions (1)-(3) (in cm3 molecule −1s−1) and for the product branching ratios of reactions (1) and (2) as a function of temperature (all errors 1σ) The calculated rate coefficients for reactions (1)-(3) at 298 K are therefore (in 10−13 cm3molecule −1s −1 23 ± 2, 6.7 ± 1.3, and 0.040 ± 0.012, respectively which compare well with the values measured elsewhere at this temperature using a similar technique. The product branching ratios and the Arrhenius parameters are compared with those for other substituted and unsubstituted peroxy radical self reactions. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 323–331, 1997

The temperature dependence of the rate coefficients for β‐hydroxyperoxy radical self reactions

The temperature dependence of the rate coefficients for β‐hydroxyperoxy radical self reactions