Nature of the radical intermediates in a substituted cyclopropylcarbiny-allylcarbinyl system

We have sought to determine the nature of the free-radical precursors to ring-opened hydrocarbon 5 and ring-closed hydrocarbon 6. Reasonable alternative formulations involve the postulation of hydrogen abstraction (a) by a pair of rapidly equilibrating classical radicals (the ring-opened allylcarbinyl-type radical 3 and the ring-closed cyclopropylcarbinyl-type 4), or (b) by a nonclassical radical such as homoallylic radical 7.

[Figure not reproduced.]

Entry to the radical system is gained via degassed thermal decomposition of peresters having the ring-opened and the ring-closed structures. The ratio of 6:5 is essentially independent of the hydrogen donor concentration for decomposition of the former at 125° in the presence of triethyltin hydrdride. A deuterium labeling study showed that the α and β methylene groups in 3 (or the equivalent) are rapidly interchanged under these conditions.

Existence of two (or more) product-forming intermediates is indicated (a) by dependence of the ratio 6:5 on the tin hydride concentration for decomposition of the ring-closed perester at 10 and 35°, and (b) by formation of cage products having largely or wholly the structure (ring-opened or ring-closed) of the starting perester.

Relative rates of hydrogen abstraction by 3 could be inferred by comparison of ratios of rate constants for hydrogen abstraction and ortho-ring cyclization:

[Figure not reproduced.]

At 100° values of k_a/k_r are 0.14 for hydrogen abstraction from 1,4-cyclohexadiene and 7 for abstraction from triethyltin hydride. The ratio 6:5 at the same temperature is ~0.0035 for hydrogen abstraction from 1,4-cyclohexadiene, ~0.078 for abstraction from the tin hydride, and ≥ 5 for abstraction from cyclohexadienyl radicals. These data indicate that abstraction of hydrogen from triethyltin hydride is more rapid than from 1,4-cyclohexadiene by a factor of ~1000 for 4, but only ~50 for 3.

Measurements of product ratios at several temperatures allowed the construction of an approximate energy-level scheme. A major inference is that isomerization of 3 to 4 is exothermic by 8 ± 3 kcal/mole, in good agreement with expectations based on bond dissociation energies. Absolute rate-constant estimates are also given.

The results are nicely compatible with a classical-radical mechanism, but attempted interpretation in terms of a nonclassical radical precursor of product ratios formed even from equilibrated radical intermediates leads, it is argued, to serious difficulties.

The roles played by hydrogen abstraction from 1,4,-cyclohexadiene and from the derived cyclohexadienyl radicals were probed by fitting observed ratios of 6:5 and 5:10 in the sense of least-squares to expressions derived for a complex mechanistic scheme. Some 30 to 40 measurements on each product ratio, obtained under a variety of experimental conditions, could be fit with an average deviation of ~6%. Significant systematic deviations were found, but these could largely be redressed by assuming (a) that the rate constant for reaction of 4 with cyclohexadienyl radical is inversely proportional to the viscosity of the medium (i.e., is diffusion-controlled), and (b) that k_a/k_r for hydrogen abstraction from 1,4-cyclohexadiene depends slightly on the composition of the medium. An average deviation of 4.4% was thereby attained.

Degassed thermal decomposition of the ring-opened perester in the presence of the triethyltin hydride occurs primarily by attack on perester of triethyltin radicals, presumably at the –O-O- bond, even at 0.01 M tin hydride at 100 and 125°. Tin ester and tin ether are apparently formed in closely similar amounts under these conditions, but the tin ester predominates at room temperature in the companion air-induced decomposition, indicating that attack on perester to give the tin ether requires an activation energy approximately 5 kcal/mole in excess of that for the formation of tin ester.

O herói e o inimigo no imaginário do jacobinismo brasileiro 1894/1897

Esta dissertação tem como objetivo compreender e analisar o jacobinismo brasileiro tendo como foco os anos de 1894 até 1897. Pretende-se perceber como esse grupo conseguiu construir um projeto de personalização do poder em torno do Marechal Floriano Peixoto em momentos críticos da história República brasileira: durante a Revolta da Armada de 1894; no momento de transição do governo militar para o governo civil de Prudente de Moraes em 1894/95; e na ocasião da morte do Marechal Floriano Peixoto em 1895. Para tanto, o estudo propõe uma reflexão sobre a utilização do discurso jornalístico como instrumento na fabricação da imagem dos revoltosos da Marinha como restauradores monarquistas e de Floriano como herói da República, buscando assim, perceber igualmente a dinâmica de sua elaboração e as suas repercussões na sociedade brasileira. Chegaremos a conclusão que as forças jacobinas enfraqueceram no momento do atentado a Prudente de Morais em 1897, mas seus discursos ainda tiveram eco na primeira metade do século XX na República brasileira.

Pinniped diet composition: a comparison of estimation models

Along the west coast of the United States, the potential impact of increasing pinniped populations on declining salmonid (Oncorhynchus spp.) stocks has become an issue of concern. Fisheries managers need species-specific estimates of consumption by pinnipeds to evaluate their impact on salmonid stocks. To estimate consumption, we developed a model that estimates diet composition by reconstructing prey biomass from fecal samples. We applied the model to data collected from harbor seals (Phoca vitulina) that are present year-round in the lower Columbia River where endangered stocks of salmonids pass as returning adults and as seaward-migrating smolts. Using the same data, we applied the split-sample frequency of occurrence model, which avoids reconstructing biomass by assuming that each fecal sample represents an equal volume of consumption and that within each sample each prey item represents an equal proportion of the volume. The two models for estimating diet composition yielded size-specific differences in consumption estimates that were as large as tenfold for the smallest and largest prey. Conclusions about the impact of harbor seal predation on adult salmonids, some of their largest prey species, remain uncertain without some appropriate rationale or further information (e.g. empirical captive studies) to discriminate between these models.

Predatory behaviour of a snakehead fish (Channa striatus Bloch)

The predatory behaviour of a snake-head, Channa striatus (Bloch) on Labeo rohita fingerlings was studied in the laboratory. The study was conducted with six C. striatus (120 to 210 g and 22 to 28 cm) over 24h a day for 3 weeks. Three different sizes prey of large (2.00g and 5.8cm), medium (1.30g and 4.5cm) and small (0.72g and 3.5cm) were used for the first week and then medium size prey for 2nd and 3rd weeks. All the predators preferred eating the small group of L. rohita although all three size groups of L. rohita offered were available. It was found that the prey fishes remained together aside of the aquarium from the predator. Predator first targeted a prey, drove fast towards it, the prey tried to escape from the predator's attack using a specific route and finally the predator grasped the prey on head first and then engulfed. The handling time ranged between 45 and 50 sec. The time of peak feeding was found in the morning and in the evening of day. When 2 or 3 predators were kept in one aquarium, they engaged in fighting, head on, followed by an attack on the mouth region by the dominant one, and subsequently on the pectoral fin and caudal fin of the defeating one. After 2-3 days they became habituated to remain together and did not involve themselves in fighting.

Macro - A tool to support distributed MDO

This paper addresses a new way for handling distributed design know as the Macro concept. It is based round the assumption that future design teams will become more distributed in nature as industry exploits the Internet and other integrated communication and data exchange systems. The paper notes that this concept is part of an attack on the problems associated with the total process of Distribute Multi-Disciplinary design and Optimisation. The concepts rely on the creation of distributed self-building and self-organising teams made up from members who are globally distributed. The paper describes both the approach adopted and its implementation in a prototype software system operating over the Internet. In essence the work presented is describing a novel method for implementing a distributed design process which is far from complete but which is producing challenging ideas. © 2000 by Cranfield University.

impossible differential cryptanalysis of reduced-round aria and camellia

This paper studies the security of the block ciphers ARIA and Camellia against impossible differential cryptanalysis. Our work improves the best impossible differential cryptanalysis of ARIA and Camellia known so far. The designers of ARIA expected no impossible differentials exist for 4-round ARIA. However, we found some nontrivial 4-round impossible differentials, which may lead to a possible attack on 6-round ARIA. Moreover, we found some nontrivial 8-round impossible differentials for Camellia, whereas only 7-round impossible differentials were previously known. By using the 8-round impossible differentials, we presented an attack on 12-round Camellia without FL/FL 1 layers.

对于5轮Camellia密码的Square攻击

中国计算机学会

Zodiac算法新的Square攻击

该文重新评估了Zodiac算法抗Square攻击的能力。Zodiac算法存在8轮Square区分器,该文首先根据算法的结构特性,给出了Zodiac的4个等价结构,而后利用等价结构得到了两个新的9轮Square区分器。利用新的区分器,对不同轮数的Zodiac算法实施了Square攻击,对12轮,13轮,14轮,15轮和16轮Zodiac的攻击复杂度分别为237.3,262.9,296.1,2137.1和2189.5次加密运算,选择明文数分别为210.3,211,211.6,212.1和212.6。结果表明:完整16轮192bit密钥的Zodiac算法是不抗Square攻击的。

33轮SHACAL-2的差分非线性攻击

利用SHACAL-2的一个17轮差分非线性区分器,结合被猜测子密钥空间分割的方法和快速傅立叶变换,提出了一种攻击33轮SHACAL-2的新方法.该方法攻击33轮SHACAL-2需要244的选择明文、2496.6的33轮SHACAL-2加密和2502次算术运算,攻击成功概率为99%.与已有的结果相比较,新攻击有效地提高了单密钥下SHACAL-2的攻击轮数.

Blocking Java Applets at the Firewall

This paper explores the problem of protecting a site on the Internet against hostile external Java applets while allowing trusted internal applets to run. With careful implementation, a site can be made resistant to current Java security weaknesses as well as those yet to be discovered. In addition, we describe a new attack on certain sophisticated firewalls that is most effectively realized as a Java applet.

The M/M/1 queue with mass exodus and mass arrivals when empty

An M/M/1 queue is subject to mass exodus at rate β and mass immigration at rate {αr; r≥ 1} when idle. A general resolvent approach is used to derive occupation probabilities and high-order moments. This powerful technique is not only considerably easier to apply than a standard direct attack on the forward p.g.f. equation, but it also implicitly yields necessary and sufficient conditions for recurrence, positive recurrence and transience.

Stylistics, criticism and mythrepresentation again: squaring the circle with Ray Mackay's subjective solution for all problems

This article is a response to an article by Ray Mackay (1996) which constitutes an attack on stylistic analysis in general, and the writings of the above authors and Ron Carter in particular. Mackay's article (in Language and Communication) accuses stylistics of 'scientificness' and claims that its attempt to provide objective analyses of literary texts is futile.1 We suggest that Mackay has misrepresented what stylisticians have said about objectivity, and that his understanding of objectivity, science and the nature of text-interpretative argument is seriously flawed.

The privatisation of council housing: Stock transfer and the struggle for accountable housing

A central element in the privatization of council housing has been the development of stock transfer policy. A variety of perspectives on this process have been explored including the impact on accountability relations; however, the tenants’ experience is almost completely absent from this literature. The paper develops a case study that draws on the experience of the tenants involved in a stock transfer. In the process stock transfers, and related accountability relations, are shown to be contested with tenant-led campaigns challenging this neoliberal inspired policy. The case study illustrates the power and financial resource asymmetries in transfer campaigns with a range of anti-democratic tactics employed by those pursuing the transfer. On the basis of a critique of neoliberalism, the stock transfer process is seen as an attack on the previous democratic control of council housing, which is replaced with ‘governance by experts and elites’ and private sector inspired corporate governance forms of accountability. Thus the paper seeks to answer two questions; how democratic is the transfer process and what are the long-term implications for democratic accountability in the social housing sector.

Haloalkane degradation and assimilation by Rhodococcus rhodochrous NCIMB -13064

The bacterium Rhodococcus rhodochrous NCIMB 13064, isolated from an industrial site, could use a wide range of 1-haloalkanes as sole carbon source but apparently utilized several different mechanisms simultaneously for assimilation of substrate. Catabolism of 1-chlorobutane occurred mainly by attack at the C-1 atom by a hydrolytic dehalogenase with the formation of butanol which was metabolized via butyric acid. The detection of small amounts of gamma-butyrolactone in the medium suggested that some oxygenase attack at C-4 also occurred, leading to the formation of 4-chlorobutyric acid which subsequently lactonized chemically to gamma-butyrolactone. Although 1-chlorobutane-grown cells exhibited little dehalogenase activity on 1-chloroalkanes with chain lengths above C-10, the organism utilized such compounds as growth substrates with the release of chloride. Concomitantly, gamma-butyrolactone accumulated to 1 mM in the culture medium with 1-chlorohexadecane as substrate. Traces of 4-hydroxybutyric acid were also detected. It is suggested that attack on the long-chain chloroalkane is initiated by an oxygenase at the non-halogenated end of the molecule leading to the formation of an omega-chlorofatty acid. This is degraded by beta-oxidation to 4-chlorobutyric acid which is chemically lactonized to gamma-butyrolactone which is only slowly further catabolized via 4-hydroxybutyric acid and succinic acid. However, release of chloride into the medium during growth on long-chain chloroalkanes was insufficient to account for all the halogen present in the substrate. Analysis of the fatty acid composition of 1-chlorohexadecane-grown cells indicated that chlorofatty acids comprised 75% of the total fatty acid content with C-14:0, C-16:0, C-16:1, and C-18:1 acids predominating. Thus the incorporation of 16-chlorohexadecanoic acid, the product of oxygenase attack directly into cellular lipid represents a third route of chloroalkane assimilation. This pathway accounts at least in part for the incomplete mineralization of long-chain chloroalkane substrates. This is the first report of the coexistence of a dehalogenase and the ability to incorporate long-chain haloalkanes into the lipid fraction within a single organism and raises important questions regarding the biological treatment of haloalkane containing effluents.

GHMP Kinases - Structures, Mechanisms and Potential for Therapeutically Relevant Inhibition

The GHMP kinases are a structurally related family of small molecule kinases named after four of its members - galactokinase, homoserine kinase, mevalonate kinase and phosphomevalonate kinase. The group also includes the enzymes N-acetylgalactosamine kinase, arabinose kinase, mevalonate 5-diphosphate decarboxylase, archeal shikimate kinase and 4-(cytidine 5'-diphospho)-2-c-methyl-D-erythritol kinase. In addition the group includes two members not known to be catalytically active, the Caenorhabditis elegans sex-fate determining protein XOL-1 and the Saccharomyces cerevisiae transcriptional activator Gal3p. Two catalytic mechanisms have been proposed for GHMP kinases. The structure of mevalonate kinase suggests that an aspartate residue acts as an active site base, removing a proton from the substrate to facilitate attack on the ? phosphate of MgATP. In contrast, in homoserine kinase there is no potential catalytic base and it is proposed that catalysis is driven by transition state stabilisation. Potential chemotherapeutic interventions against GHMP kinases fall into three main categories: inhibition of galactokinase to assist suffers of galactosemia, inhibition of mevalonate kinase or mevalonate 5-diphosphate decarboxylase to reduce flux through the cholesterol biosynthesis pathway and inhibition of bacterial GHMP kinases for novel anti-microbial therapies. These are in the early stages of development, but the accumulation of structural and mechanistic data will assist future progress.