Gotowe bibliografie tematyczne / Radical

Gotowa bibliografia na temat „Radical”

Autor: Grafiati
Data publikacji: 4 czerwca 2021
Data aktualizacji: 25 maja 2024

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Artykuły w czasopismach na temat "Radical"

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Huang, Danqing, Dirk Geeraerts i Weiwei Zhang. "A diachronic analysis of the FIRE character". Chinese Semiotic Studies 17, nr 1 (14.01.2021): 1–44. http://dx.doi.org/10.1515/css-2021-0001.

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Abstract Chinese radicals are the semantic components of Chinese characters that generally indicate major concepts and categories. Characters that share the same radical may be semantically linked in various ways to the broad semantic category that the radical represents, and radicals may thus be considered a categorization mechanism to distinguish lexical meanings. Given the fact that FIRE is an independent character that can also be used as a radical in composite characters, the question arises as to what extent the semantic developments of the FIRE character and the FIRE radical are similar, i.e. does the FIRE radical develop independently of the FIRE character? Against the background of this question, this paper studies the diachronic semantic structure of the FIRE character, which will be compared to the FIRE radical in composite characters in follow-up studies. The analysis shows that the overall diachronic development of the FIRE character exhibits prototypical characteristics and a radial network structure.
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Muchnik, Pablo. "Radical Evil (radikal Böse)". Estudos Kantianos [EK] 6, nr 2 (29.01.2019): 101–6. http://dx.doi.org/10.36311/2318-0501.2018.v6n2.20.p101.

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By “evil,” Kant does not designate any set of particularly pernicious acts, but the type of volition that underlies and makes possible immorality in all its forms. The evil person, Kant believes, “makes the incentives of self-love and their inclinations the condition of compliance with the moral law –whereas it is the latter that, as the supreme condition of the satisfaction of the former, should have been incorporated into the universal maxim of the power of choice as the sole incentive” (R 6:36). This inversion of the ethical order of priority does not entail the repudiation of “the moral law (…) in rebellious attitude (by revoking obedience to it)” (R 6:36), but its conditional respect. This fraudulent relation to morality is based on complex strategies of deception, self-deception, and rationalization. The “radical “nature of these tendencies has nothing to do with the intensity or magnitude of observable wrongdoing. Evil’s radicalism is a spatial metaphor intended to designate the locus of immorality (its “root”) in an agent’s “disposition (Gesinnung). What is most baffling the Kantian view is that evil so construed is perfectly compatible with good conduct. Indeed, under the conditions of civilization, Kant believes, it is impossible to distinguish a man of good conduct from a morally good man (RGV 6:30), for the dictates of self-love generally overlap with the prescriptions of duty. The persistence of war, poverty, oppression, and the infinity of vices which cast a dark shadow over the contemporary world speak of the prescience of the Kantian approach.
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Sands, A. D. "Radicals and one-sided ideals". Proceedings of the Royal Society of Edinburgh: Section A Mathematics 103, nr 3-4 (1986): 241–51. http://dx.doi.org/10.1017/s0308210500018898.

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The correspondence between radicals of associative rings and A-radicals is studied. It is shown that corresponding to each A-radical there is an interval of radicals and that each radical belongs to exactly one such interval. The question of the nature of the radical of a one-sided ideal is considered. It is shown that the radicals such that the radical of a one-sided ideal is always a one-sided ideal are those which contain their associated A-radicals. Radicals such that the radical of a one-sided ideal always equals the intersection of a left ideal and a right ideal are described, as are those A-radicals such that every associated radical has this property.
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Kyne, Sara H., i Carl H. Schiesser. "Ab Initio Studies of Carbonyl Radical Additions to Hydrazone Systems". Australian Journal of Chemistry 62, nr 7 (2009): 728. http://dx.doi.org/10.1071/ch09165.

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Ab initio and DFT calculations reveal that intermolecular radical additions of both acyl and oxyacyl radials to hydrazones occur through SOMO → π*hydrazone, πhydrazone → SOMO and LPN → SOMO interactions between the radical and the hydrazone π-system. Both acetyl and methoxycarbonyl radicals show preference for addition to the carbon end of the carbon–nitrogen π-bond. At the highest level of theory used in this study (G2//MP2(full)/6-31G*), energy barriers of 11.2 and 22.6 kJ mol–1 are calculated for acetyl radical addition to the carbon and nitrogen-ends of N-aminomethanimine respectively. The analogous energy barriers for the methoxycarbonyl radical are 4.9 and 25.7 kJ mol–1 at the same level of theory.
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Adrian, Gerild, Edi Suryanto i Defny S. Wewengkang. "AKTIVITAS PENANGKAL RADIKAL BEBAS DARI FRAKSI KULIT KAYU SAGU BARUK (Arenga microcarpha Beccari)". PHARMACON 10, nr 1 (24.02.2021): 762. http://dx.doi.org/10.35799/pha.10.2021.32777.

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ABSTRACTThis study aims to determine the antioxidant activity and free radical antidote from fraction of bark sago baruk (Arenga microcarpha Beccari). This study initiated by extracting the powder of bark sago baruk using the maceration method for 3 days with ethanol 80%. The extract then partitioned using a series of solvent such as petroleum ether, ethyl acetate, buthanol, aquadest. The results showed that the ethyl acetate fraction had the highest free radical antidote content followed by the aquadest fraction, buthanol fraction, petroleum ether fraction. The content of free radical antidote respectively was 86,25%; 66,30%; 65,32%; 43,43%. Based on this study, the ethyl acetate fraction was the best fraction can act as an antidote to free radicals better than other fractions. Keywords: Bark sago baruk, fraction, free radical antidote ABSTRAKPenelitian ini bertujuan untuk menentukan Aktivitas penangkal radikal bebas dari fraksi kulit kayu sagu baruk (Arenga microcarpha beccari). Penelitian ini dimulai dengan mengekstraksi serbuk kulit kayu sagu baruk menggunakan cara maserasi selama 3 hari dengan pelarut etanol 80%. Ekstrak kemudian dipartisi menggunakan pelarut petroleum eter, etil asetat, butanol, dan aquades. kemudian ditentukan aktivitas antioksidan dan penangkal radikal bebas. Hasilnya menunujukan bahwa fraksi etil asetat memiliki kandungan penangkal radikal bebas tertinggi diikuti fraksi aquades, fraksi butanol, dan fraksi petroleum eter. Kandungan penangkal radikal bebas berturut-turut adalah 86,25%; 66,30%; 65,32%; 43,43%. Berdasarkan penelitian ini, dapat disimpulkan bahwa fraksi etil asetat dapat berperan sebagai penangkal radikal bebas lebih baik dibandingkan dengan fraksi lainnya. Kata Kunci: Kulit Kayu Sagu Baruk, Fraksi, Penangkal Radikal Bebas
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Kajiwara, Atsushi. "Characterizations of radicals formed in radical polymerizations and transfer reactions by electron spin resonance spectroscopy". Pure and Applied Chemistry 90, nr 8 (28.08.2018): 1237–54. http://dx.doi.org/10.1515/pac-2018-0401.

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Abstract Electron spin resonance (ESR, aka electron paramagnetic resonance, EPR) investigations have been conducted on radicals formed during radical polymerizations and provide a detailed characterization of the active radical species. Active propagating radicals can be observed during actual radical polymerizations by ESR/EPR. The chain lengths of the observed radicals were estimated by a combination of atom transfer radical polymerization (ATRP) and ESR/EPR. The structures of the chain end radicals were determined by analysis of the ESR/EPR spectra. An increase in the dihedral angles between terminal p-orbital of radical and Cβ–H bonds was observed with increasing chain lengths of methacrylate polymers. Radical transfer reactions were observed during radical polymerization of acrylates. A combination of ATRP and ESR/EPR clarified a 1,5-hydrogen shift mechanism of the radical transfer reactions using model adamantyl acrylate radicals. Penultimate unit effects were also observed. Time-resolved ESR/EPR (TR ESR) spectroscopy clarified the initiation processes of an alternating copolymerization of styrene with maleic anhydride and the copolymerization of styrene with 1,3-butadiene. Several unsolved problems in conventional radical polymerization processes have been clarified using combinations of ATRP with ESR/EPR and TR ESR. Characterization of the radicals in radical polymerizations using various ESR techniques would definitely provide interesting and useful information on conventional radical polymerizations.
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Kuznetsova, A. V., i S. V. Kuzmina. "THE EVOLUTION OF THE LEFT RADICAL PARTIES AND MOVEMENTS IN WESTERN EUROPE AND RUSSIA". KAZAN SOCIALLY-HUMANITARIAN BULLETIN 11, nr 6 (grudzień 2020): 49–53. http://dx.doi.org/10.24153/2079-5912-2020-11-6-49-53.

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A round table on the evolution of the Western European radical left parties and movements was held online on November 19, 2020. The participants of the round table presented reports and discussed such key cases of the radical left parties as Podemos, the Unconquered France and SYRIZA. In addition, they discussed what impact the Latin American experience had on the radical left in Western Europe. In the early 21st century, radial left parties and movements in Western Europe experienced an upsurge, which was largely triggered by the 2008 financial crisis. The rise of the several radial left parties was also fueled by the mass protests that continued in Europe throughout 2010. Currently, the radical left party Podemos in Spain has lost some of its supporters and faced the need to either sacrifice its principled position or be replaced by other parties. The Unconquered France also lost a significant number of votes in the 2017 elections. Finally, the most successful of the European radical left parties - SYRIZA in Greece - also lost parliamentary elections in 2019 and was forced to become the main opposition party. The roundtable participants agreed that with the rise to power, left radicals are forced to significantly change their political discourse, deradicalize and adapt to the existing rules of the game. Radical left movements in Latin America have had an undeniable impact on the Western European left. The speakers also noted that the development of the radical left ideas in Russia differs significantly from those in Western Europe. Today, the Russian radical left has no significant influence on the political arena. This article summarizes the main aspects of the academic presentations and the discussions that accompanied them.
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Sueishi, Yoshimi, Daisuke Yoshioka, Shigeru Oowada, Nobuyuki Endoh, Shunji Kohri, Hirotada Fujii, Masashi Shimmei i Yashige Kotake. "Is the Oxygen Radical Absorbance Capacity (ORAC) Method a Peroxyl-radical Scavenging Assay?" Zeitschrift für Physikalische Chemie 224, nr 06 (1.07.2010): 921–28. http://dx.doi.org/10.1524/zpch.2010.5536.

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AbstractThe oxygen radical absorbance capacity (ORAC) method employs a water soluble azo-radical initiator, AAPH (2,2’-azobis(2-amidinopropane) dihydrochloride) as a free radical generator, by which the fluorescent probe fluorescein is damaged to result in the loss of fluorescence. Antioxidants can protect the probe from the damage and the degree of protection is quantified. Because AAPH has been used as a lipid-peroxidation reagent, “oxygen radical” in ORAC is generally accepted as peroxyl radicals; however, in the present spin trapping experiments using a newly developed spin trap, CYPMPO, there was no indication of peroxyl-radical formation in AAPH decomposition in aqueous media. These spin trapping studies demonstrated that alkoxyl (RO·) radical adduct was the sole product of AAPH decomposition. In contrast, alkyl-peroxyl (ROO·) radical was spin-trapped during the decomposition of a lipid soluble azo-radical initiator AIBN (azobis(isobutyronitrile)) in non-aqueous media. We speculate that alkyl-peroxyl radicals are short-lived in water, rapidly converted into alkoxyl radicals. Although the possibility that ORAC method monitors peroxyl-radical scavenging activity cannot be completely eliminated, spin trapping evidence strongly indicates that ORAC method is a scavenging capacity assay for alkoxyl radicals.
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Nemoto, David T., Kang-Jie Bian, Shih-Chieh Kao i Julian G. West. "Radical ligand transfer: a general strategy for radical functionalization". Beilstein Journal of Organic Chemistry 19 (15.08.2023): 1225–33. http://dx.doi.org/10.3762/bjoc.19.90.

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The place of alkyl radicals in organic chemistry has changed markedly over the last several decades, evolving from challenging-to-generate “uncontrollable” species prone to side reactions to versatile reactive intermediates enabling construction of myriad C–C and C–X bonds. This maturation of free radical chemistry has been enabled by several advances, including the proliferation of efficient radical generation methods, such as hydrogen atom transfer (HAT), alkene addition, and decarboxylation. At least as important has been innovation in radical functionalization methods, including radical–polar crossover (RPC), enabling these intermediates to be engaged in productive and efficient bond-forming steps. However, direct engagement of alkyl radicals remains challenging. Among these functionalization approaches, a bio-inspired mechanistic paradigm known as radical ligand transfer (RLT) has emerged as a particularly promising and versatile means of forming new bonds catalytically to alkyl radicals. This development has been driven by several key features of RLT catalysis, including the ability to form diverse bonds (including C–X, C–N, and C–S), the use of simple earth abundant element catalysts, and the intrinsic compatibility of this approach with varied radical generation methods, including HAT, radical addition, and decarboxylation. Here, we provide an overview of the evolution of RLT catalysis from initial studies to recent advances and provide a conceptual framework we hope will inspire and enable future work using this versatile elementary step.
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Zhao, Jing, Mei Wang, Hongfang Yang, Meng Zhang, Ping Liu i Yuxiang Bu. "Radical–Radical Interactions among Oxidized Guanine Bases Including Guanine Radical Cation and Dehydrogenated Guanine Radicals". Journal of Physical Chemistry B 117, nr 37 (6.09.2013): 10698–710. http://dx.doi.org/10.1021/jp4042149.

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Rozprawy doktorskie na temat "Radical"

1

Grice, I. Darren, i n/a. "Some New Aspects of Radical Trapping Using an Aminoxyl Radical Trap". Griffith University. School of Science, 1993. http://www4.gu.edu.au:8080/adt-root/public/adt-QGU20050915.150556.

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An investigation of the initiation mechanism in the free radical copolymerisation of acrylonitrile and vinyl acetate using the aminoxyl radical trapping technique, employing 1,1 ,3,3-tetramethyl-2,3-dihydro- 1 Hisoindol-2-yloxyl is reported. Based upon the experimental results, the mechanism of initiation is suggested as proceeding via the 'free monomer' mechanism. Additionally, the effect of Lewis acids on the initiation mechanism is reported. A study of the addition of phosphorus-centred radicals to alkenes and phenylacetylene, utilising the aminoxyl radical trapping technique is reported. The results indicate a decreased rate of addition by both diphenylphosphinyl and dimethoxyphosphinyl radicals to cyclic versus acyclic alkenes. In contrast to cyclic alkenes, both these phosphorus-centred radicals add readily to the triple bond of phenylacetylene. The stereochemistry of the addition of diphenyiphosphinyl and dimethoxyphosphinyl radicals and of the aminoxyl trap is discussed. The stereochemistry of the addition of benzoyloxyl radicals to a conformationally rigid alkene, trans-a2-octalin is reported. Attempts to examine the initiation mechanism in the free radical copolymerisation of styrene/maleic anhydride and of styrene/tetracyanoethylene utilising the aminoxyl radical trapping technique are described. Also described are attempts to synthesise some new phosphorus radical initiators.
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Grice, I. Darren. "Some New Aspects of Radical Trapping Using an Aminoxyl Radical Trap". Thesis, Griffith University, 1993. http://hdl.handle.net/10072/365216.

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An investigation of the initiation mechanism in the free radical copolymerisation of acrylonitrile and vinyl acetate using the aminoxyl radical trapping technique, employing 1,1 ,3,3-tetramethyl-2,3-dihydro- 1 Hisoindol-2-yloxyl is reported. Based upon the experimental results, the mechanism of initiation is suggested as proceeding via the 'free monomer' mechanism. Additionally, the effect of Lewis acids on the initiation mechanism is reported. A study of the addition of phosphorus-centred radicals to alkenes and phenylacetylene, utilising the aminoxyl radical trapping technique is reported. The results indicate a decreased rate of addition by both diphenylphosphinyl and dimethoxyphosphinyl radicals to cyclic versus acyclic alkenes. In contrast to cyclic alkenes, both these phosphorus-centred radicals add readily to the triple bond of phenylacetylene. The stereochemistry of the addition of diphenyiphosphinyl and dimethoxyphosphinyl radicals and of the aminoxyl trap is discussed. The stereochemistry of the addition of benzoyloxyl radicals to a conformationally rigid alkene, trans-a2-octalin is reported. Attempts to examine the initiation mechanism in the free radical copolymerisation of styrene/maleic anhydride and of styrene/tetracyanoethylene utilising the aminoxyl radical trapping technique are described. Also described are attempts to synthesise some new phosphorus radical initiators.
Thesis (PhD Doctorate)
Doctor of Philosophy (PhD)
School of Science
Science, Environment, Engineering and Technology
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Shergill, Raminder. "Radicals and radical pairs in chemical and biological systems". Thesis, University of Leicester, 2010. http://hdl.handle.net/2381/11008.

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Magnetic fields of different strengths can be applied to chemical and biological systems to study processes involving radicals or radical pairs. This work uses two such techniques, electron paramagnetic resonance (EPR) spectroscopy (≥ 150 mT) in addition to time resolved EPR spectroscopy and time resolved infrared (TRIR) spectroscopy (≤ 37 mT). The former are used to monitor metalloproteins, and the photochemistry of phosphorus oxides, while TRIR spectroscopy is used to record the magnetic field effects on the reaction kinetics of neutral radical pairs. The thesis begins with an introduction and an overview of the experimental techniques and developments. This is followed by an EPR study of the Fe(III) binding proteins, transferrin and lactoferrin and the effect thereon of catecholamine stress hormones. Catecholamines mediate bacterial growth by sequestering iron from the iron binding proteins. The mechanism of iron capture is unknown, however, the current work reveals Fe(III) binding by the catecholamine and supports subsequent reduction as the most likely route. Since catecholamines are also administered therapeutically, the validity of EPR as a diagnostic technique is examined and iron loss from human serum transferrin is observed. Also within this work, experiments are presented in which TRIR spectroscopy is used to investigate factors that affect the development of magnetic field effects for radical pairs in different solutions. This initially involves studies on acylphosphine oxides. In addition to the reported photoprocesses, alternative chemistry is uncovered, which occurs when bisacylphosphine oxide is in solutions where the solvent is sufficiently nucleophilic. The photochemistry is investigated using time resolved EPR and density functional theory calculations to suggest three possible structures that are responsible for the additional radicals observed. Furthermore, encapsulated organic radical pairs in reverse micelles are studied. These experiments, in combination with dynamic light scattering measurements provide insight into the magnitude of the observed magnetic field effects and the differing kinetics of the radical pair in the reverse micelles.
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Barrera, Mora Jose Felix Fernando. "On radical extensions and radical towers". Diss., The University of Arizona, 1989. http://hdl.handle.net/10150/184833.

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Let K/F be a separable extension. (i) If K = F(α) with αⁿ ∈ F for some n, K/F is said to be a radical extension. (ii) If there exists a sequence of fields F = F₀ ⊆ F₁ ⊆ ... ⊆ F(s) = K so that Fᵢ₊₁ = Fᵢ(αᵢ) with αᵢⁿ⁽ⁱ⁾ ∈ Fᵢ for some nᵢ ∈ N, charF ∧nᵢ for every i, and [Fᵢ₊₁ : Fᵢ] = nᵢ, K/F is said to be a radical tower. In the first part of this work, we present two theorems which give sufficient conditions for a field extension K/F to be radical. In the second part, we present results which provide conditions under which every subfield of a radical tower is also a radical tower.
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Fabbri, Claudia. "Mechanistic aspects of lignin degradation. Role of radicals and radical ions". Doctoral thesis, La Sapienza, 2005. http://hdl.handle.net/11573/917334.

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Ishaq, Ahtsham. "The development and use of novel green radical methodology". Thesis, University of Aberdeen, 2010. http://digitool.abdn.ac.uk:80/webclient/DeliveryManager?pid=158370.

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Over the last forty years the steady use of radical reactions as the key steps in syntheses has increased. The most commonly used radical reagent is tributyl tinhydride. However such tin based radical reagents are toxic and often contaminate the product as they are difficult to remove. As an alternative to these tin reagents, a novel NaBH4/U.V. system was developed. This system was successfully used to effect the radical reduction of various aromatic halides. In light of these results it was thought that other useful transformations such as C-C bond formation could be achieved. Radical cyclisation onto unsaturated bonds, halogen atom transfers radical cyclisation (HATRC) and 1-5 hydrogen atom translocations were explored. This, 1-5 hydrogen atom translocations, methodology has been successfully applied to the synthesis of the spirocyclic natural products (±) horsfiline and coerulescine. With this success the use of the NaBH4/U.V. system on pyridine substrates was explored. Unfortunately this was not achieved with our current understanding of this reaction. However the use of tributylgernamium hydride, which is considered a ‘green’ radical reagent when compared to tin based reagents, proved successful. The novel application of this reagent in the 1-5 hydrogen atom transfer reaction on pyridine substrates was successfully demonstrated. Its use was successfully employed in the synthesis of a pyridine based bioisostere derivative of horsfiline.
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McGarry, Peter F. "Radical and radical-like reactions of (1.1.1);propellane". Thesis, University of Ottawa (Canada), 1992. http://hdl.handle.net/10393/7811.

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(1.1.1) Propopellane, I, is the ultimate propellane in terms of its small size and the inversion of the tetrahedral geometry about its bridgehead carbons. As such I is reactive towards radicals and carbenes. We have studied the kinetics and mechanisms of reaction of various carbon and heteroatom centered free radicals with I by nanosecond flash photolysis and product studies techniques.(DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI) The addition of diphenylcarbene (DPC) and phenylchlorocarbene (PCC) to I have also been investigated. Addition of DPC proceeds via a 1,4-biradical intermediate, II, whereas with PCC it appears that the final product, III, is formed directly upon reaction. The implications of the apparent concerted addition of the singlet carbene to I are discussed.(DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI) The role of I as a quencher of electronic excited states is also reported.
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Botelho, João Francisco. "Epigênese radical". Florianópolis, SC, 2007. http://repositorio.ufsc.br/xmlui/handle/123456789/89646.

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Dissertação (mestrado) - Universidade Federal de Santa Catarina, Centro de Filosofia e Ciências Humanas. Programa de Pós-graduação em Filosofia.
Made available in DSpace on 2012-10-23T00:56:48Z (GMT). No. of bitstreams: 0
Existe na biologia contemporânea um consenso de que a genética proporcionou uma solução conciliatória para o longo debate entre preformacionistas e epigenesistas. O desenvolvimento, segundo a genética, é um processo híbrido de preformação e epigênese. A preformação persiste como informação, como um programa codificado do desenvolvimento. A epigênese persiste como a tradução do programa genético, como a revelação da informação pela expressão gênica. O presente trabalho critica esta conciliação genética a partir de duas análises epistemológicas # uma histórica e a outra conceitual # e defende uma posição alternativa # a Perspectiva dos Sistemas Desenvolvimentais (PSD). A análise histórica consiste em mostrar que o conceito de preformação é mais amplo e plástico do que a simples idéia de preexistência e pré-delineação de um organismo completo. O conceito de preformação chega ao século XX associado ao conceito de unidades hereditárias determinantes do desenvolvimento e está historicamente associado à tradição de pesquisa genética. A análise conceitual consiste em mostrar que a biologia contemporânea desautoriza o discurso preformacionista contido nas idéias de herança como transmissão genética, primazia e independência causal dos genes, herança sólida e programa genético. No lugar da conciliação genética defendo uma perspectiva estritamente epigenética dos processos celulares e desenvolvimentais como proposta pela PSD. There is a consensus in contemporary biology that genetics provided a conciliatory solution for the long-standing debate between preformationists and epigenesists. Development, according to the genetic conciliation, is a hybrid process of preformation and epigenesis. Preformation persists as information, as a codified program of development. Epigenesis persists as the translation of the genetic program, as the revelation of genetic information. The present thesis criticizes this genetic conciliation from two epistemological points of view # a historical one and a conceptual one # and supports an alternative position: the Developmental Systems Perspective (DSP). The historical analysis shows that the preformation tradition is wider than the simple idea of preexistence and pre-delineation of form. The preformation tradition arrives at the 20th century associated to the concept of units of inheritance controlling development and it is historically associated with the research tradition of genetics. The conceptual analysis consists of showing that contemporary biology discourages the preformationists assumptions enclosed in the ideas of heredity as genetic transmission, causal priority of the genes, exclusively genetic inheritance and genetic program. In the place of the genetic conciliation, we defend a strict epigenetic view of cellular and developmental processes, coherent with the DSP.
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Qureshi, Tariq. "Spin chemistry". Thesis, University of Oxford, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.365292.

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Wood, Geoffrey Paul Farra. "Theoretical Investigations of Radical-Mediated Protein Oxidation". Thesis, The University of Sydney, 2006. http://hdl.handle.net/2123/1413.

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This thesis primarily details the application of high-level ab initio quantum chemistry techniques in order to understand aspects of free-radical mediated protein oxidation. Traditionally, product analysis and electron paramagnetic resonance (EPR) spectroscopy are the primary means for elucidating the chemistry of protein oxidation. However, in experiments involving relatively small proteins reacting with a controlled radical-flux, a vast array of compounds can be produced, which are often difficult to analyse. Quantum chemical techniques on the other hand, can calculate the properties of any particular species directly, without suffering from the problems associated with experiment, such as side-reactions and chain processes. The results presented in this thesis are aimed at elucidating mechanistic details of protein oxidation, which might otherwise be difficult to probe experimentally. Chapter 1 gives an overview of the free-radical hypothesis of disease and ageing. Protein-derived radicals can undergo a variety of reactions, with the particular reaction that occurs depending on numerous aspects. Many types of reactions have been identified through radiolysis experiments of amino acids, and these are detailed in this chapter. In addition, the key reactive species are characterized and their different chemistries explained. Chapter 2 details the theoretical tools used throughout this thesis. Species with unpaired electrons (radicals) present unique problems for quantum chemistry to handle, thus an appropriate choice of theoretical technique is needed. The approach taken in this thesis is to use high-level compound methods, many of which have been directly formulated to give improved results for radical species, to provide benchmark quality results by which other less demanding techniques can be assessed. During the course of this study, it became apparent there was a void in the armoury of tools that could be used for the theoretical chemistry calculations. Chapter 3 details the formulation of a new tool in an attempt to fill this gap. Historically, the formulation of this new procedure came after much of the work in this thesis had been carried out. Thus, for the study of many of the reactions of this thesis the new method has not been used. However, it is most appropriate to place its formulation after summarizing the current status of techniques in common use today. Chapters 4 and 5 detail computations carried out on models of peptides containing backbone carbon- and nitrogen-centered radicals. A number of different theoretical techniques are used in these chapters, ranging from the highly accurate and computationally intensive to the less reliable and less demanding. The highly accurate techniques are used to gauge the accuracy of the other less demanding theoretical techniques so that the latter can be used with confidence in larger systems. Not only is the choice of theoretical technique important but also the judicious choice of model is essential. With this in mind, models are incrementally built until convergence of the particular property of interest is reached. Chapters 6 and 7 detail the calculations of β-scission reactions of alkoxyl radicals, which are a particular class of reaction known to occur on peptide backbones. Alkoxyl radicals are particularly difficult for theory to describe correctly. Therefore, Chapter 6 extensively assesses and then identifies the theoretical methods needed to portray them. Chapter 7 uses the techniques identified in the previous chapter in order to predict how the preference for a particular type of β-scission reaction changes.
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Książki na temat "Radical"

1

Radical graphics/graphic radicals. San Francisco: Chronicle Books, 1999.

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Bockstal, Koen van. Radicale ensembles: Radical ensembles. Brussel: Academic & Scientific Publishers, 2018.

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Werner, Fenz, Braun Reinhard, Neue Galerie am Landesmuseum Joanneum. i Künstlerhaus (Graz Austria), red. Radikale Bilder = Radical images. Graz: Edition Camera Austria, 1996.

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Guía radical. Buenos Aires: Editorial Galerna, 1986.

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Paulauskas, Irena O. Radical polymerization: New developments. Hauppauge, N.Y: Nova Science Publishers, 2011.

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Canadian Broadcasting Corporation. Radical preachers, radical politics. Montreal: CBC Transcripts, 1985.

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Fischer, H., red. Inorganic Radicals, Radical Ions and Radicals in Metal Complexes. Berlin/Heidelberg: Springer-Verlag, 1987. http://dx.doi.org/10.1007/b32561.

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Radical chemistry. New York: Ellis Horwood, 1994.

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Perkins, M. John. Radical chemistry. New York: Ellis Horwood, 1994.

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Forbes, Malcolm D. E., red. Carbon-Centered Free Radicals and Radical Cations. Hoboken, NJ, USA: John Wiley & Sons, Inc., 2009. http://dx.doi.org/10.1002/9780470584118.

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Części książek na temat "Radical"

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Gaskell, Michael S. "Radical Communication = Radical Change". W Radical Principals, 65–84. New York: Routledge, 2022. http://dx.doi.org/10.4324/9781003275718-5.

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Charnley, Steven. "Radical". W Encyclopedia of Astrobiology, 1413. Berlin, Heidelberg: Springer Berlin Heidelberg, 2011. http://dx.doi.org/10.1007/978-3-642-11274-4_1338.

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Gooch, Jan W. "Radical". W Encyclopedic Dictionary of Polymers, 606. New York, NY: Springer New York, 2011. http://dx.doi.org/10.1007/978-1-4419-6247-8_9731.

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Charnley, Steven B. "Radical". W Encyclopedia of Astrobiology, 2124. Berlin, Heidelberg: Springer Berlin Heidelberg, 2015. http://dx.doi.org/10.1007/978-3-662-44185-5_1338.

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Charnley, Steven B. "Radical". W Encyclopedia of Astrobiology, 1. Berlin, Heidelberg: Springer Berlin Heidelberg, 2014. http://dx.doi.org/10.1007/978-3-642-27833-4_1338-3.

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Charnley, Steven B. "Radical". W Encyclopedia of Astrobiology, 2595–96. Berlin, Heidelberg: Springer Berlin Heidelberg, 2023. http://dx.doi.org/10.1007/978-3-662-65093-6_1338.

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Chung, Benjamin I., i John A. Libertino. "Radical Nephrectomy". W Clinical Management of Renal Tumors, 177–94. Totowa, NJ: Humana Press, 2008. http://dx.doi.org/10.1007/978-1-60327-149-3_11.

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Cross, Mary. "Radical Syntax". W Henry James, 1–18. London: Palgrave Macmillan UK, 1993. http://dx.doi.org/10.1007/978-1-349-22661-0_1.

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Tress, W. "“Radical interpretation”". W Sprache — Person — Krankheit, 1–16. Berlin, Heidelberg: Springer Berlin Heidelberg, 1987. http://dx.doi.org/10.1007/978-3-642-71696-6_1.

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Drozd, Yurij A., i Vladimir V. Kirichenko. "The Radical". W Finite Dimensional Algebras, 44–68. Berlin, Heidelberg: Springer Berlin Heidelberg, 1994. http://dx.doi.org/10.1007/978-3-642-76244-4_3.

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Streszczenia konferencji na temat "Radical"

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Blanchard, Rebecca. "“Militant or moderate? Abd al Malik’s literary representations of the French banlieue”". W Action radicale, sujet radical : racines, représentations, symboles et créations = Radical action, radical subject : roots, representations, symbols and creations. Éditions de l'Université de Sherbrooke, 2015. http://dx.doi.org/10.17118/11143/8369.

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Spiegel, Jennifer. "Of spectacle and collective resistance: rethinking the relationships between “symbolic” and “direct” action". W Action radicale, sujet radical : racines, représentations, symboles et créations = Radical action, radical subject : roots, representations, symbols and creations. Éditions de l'Université de Sherbrooke, 2015. http://dx.doi.org/10.17118/11143/8370.

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Vien, Myriam. "Entre la poésie et le terrorisme : La Grande Tribu : c’est la faute à Papineau de Victor-Lévy Beaulieu". W Action radicale, sujet radical : racines, représentations, symboles et créations = Radical action, radical subject : roots, representations, symbols and creations. Éditions de l'Université de Sherbrooke, 2015. http://dx.doi.org/10.17118/11143/8371.

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Fortier, Michaël. "La Fabrication d’un radical : Léon Bloy, « entrepreneur de démolitions »". W Action radicale, sujet radical : racines, représentations, symboles et créations = Radical action, radical subject : roots, representations, symbols and creations. Éditions de l'Université de Sherbrooke, 2015. http://dx.doi.org/10.17118/11143/8372.

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Dumont, Catherine. "Du Masculin au féminin au masculin : transgressions identitaires et sexuelles dans Self de Yann Martel". W Action radicale, sujet radical : racines, représentations, symboles et créations = Radical action, radical subject : roots, representations, symbols and creations. Éditions de l'Université de Sherbrooke, 2015. http://dx.doi.org/10.17118/11143/8373.

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Landry, Vincent. "Autofiction théorique queer : mélange dans le(s) genre(s)". W Action radicale, sujet radical : racines, représentations, symboles et créations = Radical action, radical subject : roots, representations, symbols and creations. Éditions de l'Université de Sherbrooke, 2015. http://dx.doi.org/10.17118/11143/8374.

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Boisvenue, Jean-François. "L’Iconoclasme de Nous Sommes Tous Art". W Action radicale, sujet radical : racines, représentations, symboles et créations = Radical action, radical subject : roots, representations, symbols and creations. Éditions de l'Université de Sherbrooke, 2015. http://dx.doi.org/10.17118/11143/8375.

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Matte, Hélène. "Desseins : le dessin comme posture performative où la contemplation s’avère aussi une forme d’action". W Action radicale, sujet radical : racines, représentations, symboles et créations = Radical action, radical subject : roots, representations, symbols and creations. Éditions de l'Université de Sherbrooke, 2015. http://dx.doi.org/10.17118/11143/8376.

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Malish, Sherrie. "Overturning the common sense of capitalism: why the occupy movement’s diffused agenda may have been its greatest strength". W Action radicale, sujet radical : racines, représentations, symboles et créations = Radical action, radical subject : roots, representations, symbols and creations. Éditions de l'Université de Sherbrooke, 2015. http://dx.doi.org/10.17118/11143/8368.

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Corbett, Nicole. "Rousseau’s radical idealism: or how to better the world through duplicitous means". W Action radicale, sujet radical : racines, représentations, symboles et créations = Radical action, radical subject : roots, representations, symbols and creations. Éditions de l'Université de Sherbrooke, 2015. http://dx.doi.org/10.17118/11143/8365.

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Raporty organizacyjne na temat "Radical"

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Williams, T. F. Studies of radiation-produced radicals and radical ions. Office of Scientific and Technical Information (OSTI), styczeń 1991. http://dx.doi.org/10.2172/5420713.

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Yeager, Peter E. Radical Islam. Fort Belvoir, VA: Defense Technical Information Center, lipiec 2002. http://dx.doi.org/10.21236/ada406226.

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Schneider, Barry R. Radical Responses to Radical Regimes: Evaluating Preemptive Counter-Proliferation. Fort Belvoir, VA: Defense Technical Information Center, maj 1995. http://dx.doi.org/10.21236/ada421973.

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Burke, Steven. Radical Improvements Require Radical Actions: Simulating a High-Maturity Software Organization. Fort Belvoir, VA: Defense Technical Information Center, czerwiec 1997. http://dx.doi.org/10.21236/ada327609.

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Glassman, I., i K. Brezinsky. Aromatic-radical oxidation chemistry. Office of Scientific and Technical Information (OSTI), styczeń 1993. http://dx.doi.org/10.2172/6579384.

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Rochester, Mark. Partial versus radical nephrectomy. BJUI Knowledge, maj 2021. http://dx.doi.org/10.18591/bjuik.0102.v2.

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Nandi, Arindam, Nicole Haberland i Thoai Ngo. The Radical Power of Education. Population Council, grudzień 2023. http://dx.doi.org/10.31899/sbsr2023.1056.

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Dagdigian, Paul J. Spectroscopic Characterization of Free Radical Intermediates. Fort Belvoir, VA: Defense Technical Information Center, maj 2001. http://dx.doi.org/10.21236/ada394529.

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Glassman, I., i K. Brezinsky. Aromatic-radical oxidation chemistry. Progress report. Office of Scientific and Technical Information (OSTI), maj 1993. http://dx.doi.org/10.2172/10149531.

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Wang, M., J. M. Smith i B. J. McCoy. Free-radical kinetics of coal liquefaction. Office of Scientific and Technical Information (OSTI), lipiec 1994. http://dx.doi.org/10.2172/26601.

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