Justifications and limits in the politically motivated lawbreaking of environmental activist groups

In recent events, notions of political protest, civil disobedience, extremism, and criminal action have become increasingly blurred. The London Riots, the Occupy movement, and the actions of hacking group Anonymous have all sparked heated debate about the limits of legitimate protest, and the distinction between an acceptable action and a criminal offence. Long before these events, environmental activists were challenging convention in protest actions, with several groups engaging in politically motivated law-breaking. The emergence of the term ‘eco-tage’ (the sabotage of equipment in order to protect the environment) signifies the important place environmental activists hold in challenging the traditional boundaries between illegal action and legitimate protest. Many of these groups establish their own boundaries of legitimacy, with some justifying their actions on the basis of civil disobedience or extensional self-defence. This paper examines the statements of environmental activist organisations that have engaged in politically motivated law breaking. It identifies the parameters that these groups set on their illegal actions, as well as the justifications that they provide, with a view to determining where these actions fit in the vast grey area between legal protest and violent extremism.

The estrogen receptor 1 G594A polymorphism is associated with migraine susceptibility in two independent case/control groups

Migraine is a painful and debilitating disorder with a significant genetic component. Steroid hormones, in particular estrogen, have long been considered to play a role in migraine, as variations in hormone levels are associated with migraine onset in many sufferers of the disorder. Steroid hormones mediate their activity via hormone receptors, which have a wide tissue distribution. Estrogen receptors have been localized to the brain in regions considered to be involved in migraine pathogenesis. Hence it is possible that genetic variation in the estrogen receptor gene may play a role in migraine susceptibility. This study thus examined the estrogen receptor 1 (ESRα) gene for a potential role in migraine pathogenesis and susceptibility. A population-based cohort of 224 migraine sufferers and 224 matched controls were genotyped for the G594A polymorphism located in exon 8 of the ESR1 gene. Statistical analysis indicated a significant difference between migraineurs and non-migraineurs in both the allele frequencies (P=0.003) and genotype distributions (P=0.008) in this sample. An independent follow-up study was then undertaken using this marker in an additional population-based cohort of 260 migraine sufferers and 260 matched controls. This resulted in a significant association between the two groups with regard to allele frequencies (P=8×10−6) and genotype distributions (P=4×10−5). Our findings support the hypothesis that genetic variation in hormone receptors, in particular the ESR1 gene, may play a role in migraine.

Controlling whole blood activation and resultant clot properties on various material surfaces : a possible therapeutic approach for enhancing bone healing

Injured bone initiates the healing process by forming a blood clot at the damaged site. However, in severe damage, synthetic bone implants are used to provide structural integrity and restore the healing process. The implant unavoidably comes into direct contact with whole blood, leading to a blood clot formation on its surface. Despite this, most research in bone tissue engineering virtually ignores the important role of a blood clot in supporting healing. Surface chemistry of a biomaterial is a crucial property in mediating blood-biomaterials interactions, and hence the formation of the resultant blood clot. Surfaces presenting mixtures of functional groups carboxyl (–COOH) and methyl (–CH3) have been shown to enhance platelet response and coagulation activation, leading to the formation of fibrin fibres. In addition, it has been shown that varying the compositions of these functional groups and the length of alkyl groups further modulate the immune complement response. In this study, we hypothesised that a biomaterial surface with mixture of –COOH/–CH3(methyl), –CH2CH3 (ethyl) or –(CH2)3CH3 (butyl) groups at different ratios would modulate blood coagulation and complement activation, and eventually tailor the structural and functional properties of the blood clot formed on the surface, which subsequently impacts new bone formation. Firstly, we synthesised a series of materials composed of acrylic acid (AA), and methyl (MMA), ethyl (EMA) or butyl methacrylates (BMA) at different ratios and coated on the inner surfaces of incubation vials. Our surface analysis showed that the amount of –COOH groups on the surface coatings was lower than the ratios of AA prepared in the materials even though the surface content of –COOH groups increased with increasing in AA ratios. It was indicated that the surface hydrophobicity increased with increasing alkyl chain length: –CH 3 > –CH2CH3 > –(CH2)3CH3, and decreased with increasing –COOH groups. No significant differences in surface hydrophobicity was found on surfaces with –CH3 and –CH2CH3 groups in the presence of –COOH groups. The material coating was as smooth as uncoated glass and without any major flaws. The average roughness of material-coated surface (3.99 ± 0.54 nm) was slightly higher than that of uncoated glass surface (2.22 ± 0.29 nm). However, no significant differences in surface average roughness was found among surfaces with the same functionalities at different –COOH ratios nor among surfaces with different alkyl groups but the same –COOH ratios. These suggested that the surface functional groups and their compositions had a combined effect on modulating surface hydrophobicity but not surface roughness. The second part of our study was to investigate the effect of surface functional groups and their compositions on blood cascade activation and structural properties of the formed clots. It was found that surfaces with –COOH/–(CH2)3CH3 induced a faster coagulation activation than those with –COOH/–CH3 and –CH2CH3, regardless of the –COOH ratios. An increase in –COOH ratios on –COOH/–CH3 and –CH2CH3 surfaces decreased the rate of activation. Moreover, all material-coated surfaces markedly reduced the complement activation compared to uncoated glass surfaces, and the pattern of complement activation was entirely similar to that of surface-induced coagulation, suggesting there is an interaction between two cascades. The clots formed on material-coated surfaces had thicker fibrin with a tighter network at the exterior when compared to uncoated glass surfaces. Compared to the clot exteriors, thicker fibrins with a loose network were found in clot interiors. Coated surfaces resulted in more rigid clots with a significantly slower fibrinolysis after 1 h of lysis when compared to uncoated glass surfaces. Significant differences in fibrinolysis after 1 h of lysis among clots on material-coated surfaces correlated well with the differences in fibrin thickness and density at clot exterior. In addition, more growth factors were released during clot formation than during clot lysis. From an intact clot, there was a correlation between the amount of PDGF-AB release and fibrin density. Highest amount of PDGF-AB was released from clots formed on surfaces with 40% –COOH/60% –CH 3 (i.e. 65MMA). During clot lysis, the release of PDGF-AB also correlated with the fibrinolytic rate while the release of TGF-â1 was influenced by the fibrin thickness. This suggested that different clot structures led to different release profiles of growth factors in clot intact and degrading stages. We further validated whether the clots formed on material-coatings provide the microenvironment for improved bone healing by using a rabbit femoral defect model. In this pilot study, the implantation of clots formed on 65MMA coatings significantly increased new bone formation with enhanced chondrogenesis, osteoblasts activity and vascularisation, but decreased inflammatory macrophage number at the defects after 4 weeks when compared to commercial bone grafts ChronOSTM â-TCP granules. Empty defects were observed when blood clot formation was inhibited. In summary, our study demonstrated that surface functional groups and their relative ratios on material coatings synergistically modulate activation of blood cascades, resultant fibrin architecture, rigidity, susceptibility to fibrinolysis as well as growth factor release of the formed clots, which ultimately alter the healing microenvironment of injured bones.

Study of the initial stage of solid electrolyte interphase formation upon chemical reaction of lithium metal and N-Methyl-N-Propyl-Pyrrolidinium-Bis (Fluorosulfonyl) Imide

Chemical reaction studies of N-methyl-N-propyl-pyrrolidinium-bis(fluorosulfonyl)imide-based ionic liquid with the lithium metal surface were performed using ab initio molecular dynamics (aMD) simulations and X-ray Photoelectron Spectroscopy (XPS). The molecular dynamics simulations showed rapid and spontaneous decomposition of the ionic liquid anion, with subsequent formation of long-lived species such as lithium fluoride. The simulations also revealed the cation to retain its structure by generally moving away from the lithium surface. The XPS experiments showed evidence of decomposition of the anion, consistent with the aMD simulations and also of cation decomposition and it is envisaged that this is due to the longer time scale for the XPS experiment compared to the time scale of the aMD simulation. Overall experimental results confirm the majority of species suggested by the simulation. The rapid chemical decomposition of the ionic liquid was shown to form a solid electrolyte interphase composed of the breakdown products of the ionic liquid components in the absence of an applied voltage.

Interocular corneal symmetry in refractive error groups

Purpose: To examine between eye differences in corneal higher order aberrations and topographical characteristics in a range of refractive error groups. Methods: One hundred and seventy subjects were recruited including; 50 emmetropic isometropes, 48 myopic isometropes (spherical equivalent anisometropia ≤ 0.75 D), 50 myopic anisometropes (spherical equivalent anisometropia ≥ 1.00 D) and 22 keratoconics. The corneal topography of each eye was captured using the E300 videokeratoscope (Medmont, Victoria, Australia) and analyzed using custom written software. All left eye data were rotated about the vertical midline to account for enantiomorphism. Corneal height data were used to calculate the corneal wavefront error using a ray tracing procedure and fit with Zernike polynomials (up to and including the eighth radial order). The wavefront was centred on the line of sight by using the pupil offset value from the pupil detection function in the videokeratoscope. Refractive power maps were analysed to assess corneal sphero-cylindrical power vectors. Differences between the more myopic (or more advanced eye for keratoconics) and the less myopic (advanced) eye were examined. Results: Over a 6 mm diameter, the cornea of the more myopic eye was significantly steeper (refractive power vector M) compared to the fellow eye in both anisometropes (0.10 ± 0.27 D steeper, p = 0.01) and keratoconics (2.54 ± 2.32 D steeper, p < 0.001) while no significant interocular difference was observed for isometropic emmetropes (-0.03 ± 0.32 D) or isometropic myopes (0.02 ± 0.30 D) (both p > 0.05). In keratoconic eyes, the between eye difference in corneal refractive power was greatest inferiorly (associated with cone location). Similarly, in myopic anisometropes, the more myopic eye displayed a central region of significant inferior corneal steepening (0.15 ± 0.42 D steeper) relative to the fellow eye (p = 0.01). Significant interocular differences in higher order aberrations were only observed in the keratoconic group for; vertical trefoil C(3,-3), horizontal coma C(3,1) secondary astigmatism along 45 C(4, -2) (p < 0.05) and vertical coma C(3,-1) (p < 0.001). The interocular difference in vertical pupil decentration (relative to the corneal vertex normal) increased with between eye asymmetry in refraction (isometropia 0.00 ± 0.09, anisometropia 0.03 ± 0.15 and keratoconus 0.08 ± 0.16 mm) as did the interocular difference in corneal vertical coma C (3,-1) (isometropia -0.006 ± 0.142, anisometropia -0.037 ± 0.195 and keratoconus -1.243 ± 0.936 μm) but only reached statistical significance for pair-wise comparisons between the isometropic and keratoconic groups. Conclusions: There is a high degree of corneal symmetry between the fellow eyes of myopic and emmetropic isometropes. Interocular differences in corneal topography and higher order aberrations are more apparent in myopic anisometropes and keratoconics due to regional (primarily inferior) differences in topography and between eye differences in vertical pupil decentration relative to the corneal vertex normal. Interocular asymmetries in corneal optics appear to be associated with anisometropic refractive development.

Controlling whole blood activation and resultant clot properties by carboxyl and alkyl functional groups on material surfaces : a possible therapeutic approach for enhancing bone healing

Most research virtually ignores the important role of a blood clot in supporting bone healing. In this study, we investigated the effects of surface functional groups carboxyl and alkyl on whole blood coagulation, complement activation and blood clot formation. We synthesised and tested a series of materials with different ratios of carboxyl (–COOH) and alkyl (–CH3, –CH2CH3 and –(CH2)3CH3) groups. We found that surfaces with –COOH/–(CH2)3CH3 induced a faster coagulation activation than those with –COOH/– CH3 and –CH2CH3, regardless of the –COOH ratios. An increase in –COOH ratios on –COOH/–CH3 and –CH2CH3 surfaces decreased the rate of coagulation activation. The pattern of complement activation was entirely similar to that of surface-induced coagulation. All material coated surfaces resulted in clots with thicker fibrin in a denser network at the clot/material interface and a significantly slower initial fibrinolysis when compared to uncoated glass surfaces. The amounts of platelet-derived growth factor-AB (PDGF-AB) and transforming growth factor-b (TGF-b1) released from an intact clot were higher than a lysed clot. The release of PDGF-AB was found to be correlated with the fibrin density. This study demonstrated that surface chemistry can significantly influence the activation of blood coagulation and complement system, resultant clot structure, susceptibility to fibrinolysis as well as release of growth factors, which are important factors determining the bone healing process.

Short signature without random oracles and the SDH assumption in bilinear groups

We describe a short signature scheme that is strongly existentially unforgeable under an adaptive chosen message attack in the standard security model. Our construction works in groups equipped with an efficient bilinear map, or, more generally, an algorithm for the Decision Diffie-Hellman problem. The security of our scheme depends on a new intractability assumption we call Strong Diffie-Hellman (SDH), by analogy to the Strong RSA assumption with which it shares many properties. Signature generation in our system is fast and the resulting signatures are as short as DSA signatures for comparable security. We give a tight reduction proving that our scheme is secure in any group in which the SDH assumption holds, without relying on the random oracle model.

Graph coloring applied to secure computation in non-Abelian groups

We study the natural problem of secure n-party computation (in the computationally unbounded attack model) of circuits over an arbitrary finite non-Abelian group (G,⋅), which we call G-circuits. Besides its intrinsic interest, this problem is also motivating by a completeness result of Barrington, stating that such protocols can be applied for general secure computation of arbitrary functions. For flexibility, we are interested in protocols which only require black-box access to the group G (i.e. the only computations performed by players in the protocol are a group operation, a group inverse, or sampling a uniformly random group element). Our investigations focus on the passive adversarial model, where up to t of the n participating parties are corrupted.

Active security in multiparty computation over black-box groups

Most previous work on unconditionally secure multiparty computation has focused on computing over a finite field (or ring). Multiparty computation over other algebraic structures has not received much attention, but is an interesting topic whose study may provide new and improved tools for certain applications. At CRYPTO 2007, Desmedt et al introduced a construction for a passive-secure multiparty multiplication protocol for black-box groups, reducing it to a certain graph coloring problem, leaving as an open problem to achieve security against active attacks. We present the first n-party protocol for unconditionally secure multiparty computation over a black-box group which is secure under an active attack model, tolerating any adversary structure Δ satisfying the Q 3 property (in which no union of three subsets from Δ covers the whole player set), which is known to be necessary for achieving security in the active setting. Our protocol uses Maurer’s Verifiable Secret Sharing (VSS) but preserves the essential simplicity of the graph-based approach of Desmedt et al, which avoids each shareholder having to rerun the full VSS protocol after each local computation. A corollary of our result is a new active-secure protocol for general multiparty computation of an arbitrary Boolean circuit.

Gas-phase reactions of aryl radicals with 2-butyne : an experimental and theoretical investigation employing the N-methyl-pyridinium-4-yl radical cation

Aromatic radicals form in a variety of reacting gas-phase systems, where their molecular weight growth reactions with unsaturated hydrocarbons are of considerable importance. We have investigated the ion-molecule reaction of the aromatic distonic N-methyl-pyridinium-4-yl (NMP) radical cation with 2-butyne (CH3C CCH3) using ion trap mass spectrometry. Comparison is made to high-level ab initio energy surfaces for the reaction of NMP and for the neutral phenyl radical system. The NMP radical cation reacts rapidly with 2-butyne at ambient temperature, due to the apparent absence of any barrier. The activated vinyl radical adduct predominantly dissociates via loss of a H atom, with lesser amounts of CH3 loss. High-resolution Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry allows us to identify small quantities of the collisionally deactivated reaction adduct. Statistical reaction rate theory calculations (master equation/RRKM theory) on the NMP + 2-butyne system support our experimental findings, and indicate a mechanism that predominantly involves an allylic resonance-stabilized radical formed via H atom shuttling between the aromatic ring and the C-4 side-chain, followed by cyclization and/or low-energy H atom beta-scission reactions. A similar mechanism is demonstrated for the neutral phenyl radical (Ph center dot)+2-butyne reaction, forming products that include 3-methylindene. The collisionally deactivated reaction adduct is predicted to be quenched in the form of a resonance-stabilized methylphenylallyl radical. Experiments using a 2,5-dichloro substituted methyl-pyridiniumyl radical cation revealed that in this case CH3 loss from the 2-butyne adduct is favoured over H atom loss, verifying the key role of ortho H atoms, and the shuttling mechanism, in the reactions of aromatic radicals with alkynes. As well as being useful phenyl radical analogues, pyridiniumyl radical cations may form in the ionosphere of Titan, where they could undergo rapid molecular weight growth reactions to yield polycyclic aromatic nitrogen hydrocarbons (PANHs).

Development of polymers for Non-CAR resists for EUV lithography

Three strategies for approaching the design and synthesis of non-chemically amplified resists (non-CARs) are presented. These are linear polycarbonates, star polyester-blk-poly(methyl methacrylate) and comb polymers with polysulfone backbones. The linear polycarbonates were designed to cleave when irradiated with 92 eV photons and high Tg alicyclic groups were incorporated into the backbone to increase Tg and etch resistance. The star block copolymers were designed to have a core that is sensitive to 92 eV photons and arms that have the potential to provide properties such as high Tg and etch resistance. Similarly the polysulfone comb polymers were designed to have an easily degradable polymer backbone and comb-arms that impart favorable physical properties. Initial patterning results are presented for a number of the systems.

The loss of CO from the ortho, meta and para forms of deprotonated methyl benzoate in the gas phase

The ortho, meta and para anions of methyl benzoate may be made in the source of a mass spectrometer by the S(N)2(Si) reactions between HO- and methyl (o-, m-, and p-trimethylsilyl)benzoate respectively. All three anions lose CO upon collisional activation to form the ortho anion of anisole in the ratio ortho>>meta > para. The rearrangement process is charge directed through the ortho anion. Theoretical calculations at the B3LYP/6-311++G(d,p)//HF/6-31+G(d) level of theory indicate that the conversion of the meta and para anions to the ortho anion prior to loss of CO involve 1,2-H transfer(s), rather than carbon scrambling of the methoxycarbonylphenyl anion. There are two mechanisms which can account for this rearrangement, viz. (A) cyclisation of the ortho anion centre to the carbonyl group of the ester to give a cyclic carbonyl system in which the incipient methoxide anion substitutes at one of the two equivalent ring carbons of the three membered ring to yield an intermediate which loses CO to give the ortho anion of anisole, and (B) an elimination reaction to give an intermediate benzyne-methoxycarbonyl anion complex in which the MeOCO- species acts as a MeO- donor, which then adds to benzyne to yield the ortho anion of anisole. Calculations at the B3LYP/6-311++G(d,p)//HF/6-31+G(d) level of theory indicate that (i) the barrier in the first step (the rate determining step) of process A is 87 kJ mol(-1) less than that for the synchronous benzyne process B, and (ii) there are more low frequency vibrations in the transition state for benzyne process B than for the corresponding transition state for process A. Stepwise process A has the lower barrier for the rate determining step, and the lower Arrhenius factor: we cannot differentiate between these two mechanisms on available evidence.

Photoelectron spectroscopic study of the oxyallyl diradical

The photoelectron spectrum of the oxyallyl (OXA) radical anion has been measured. The radical anion has been generated in the reaction of the atomic oxygen radical anion (O center dot-) with acetone. Three low-lying electronic states of OXA have been observed in the spectrum. Electronic structure calculations have been performed for the triplet states (B-3(2) and B-3(1)) of OXA and the ground doublet state ((2)A(2)) of the radical anion using density, functional theory (DFT). Spectral simulations have been carried out for the triplet statics based on the results of the DFT calculations. The simulation identifies a vibrational progression of the CCC bending mode of the B-3(2) state of OXA in the lower electron binding energy (eBE) portion of the spectrum. On top of the B-3(2) feature, however, the experimental spectrum exhibits additional photoelectron peaks whose angular distribution is distinct from that for the vibronic peaks of the B-3(2) state. Complete active space self-consistent field (CASSCF) method and second-order perturbation theory based on the CASSCF wave function (CASPT2) have been employed to study the lowest singlet state ((1)A(1)) of OXA. The simulation based on the results of these electronic structure calculations establishes that the overlapping peaks represent the vibrational ground level of the (1)A(1) state and its vibrational progression of the CO stretching mode. The A, state is the lowest electronic state of,OXA, and the electron affinity (EA) of OXA is 1.940 +/- 0.010 eV. The B-3(2) state is the first excited state with an electronic term energy of 55 +/- 2 meV. The widths of the vibronic peaks of the (X) over tilde (1)A(1) state are much broader than those of the (a) over tilde B-3(2) state, implying that the (1)A(1) state is indeed a transition state. The CASSCF and CASPT2 calculations suggest that the (1)A(1) state is at a potential maximum along the nuclear coordinate representing disrotatory motion of the two methylene groups, which leads to three-membered-ring formation, i.e., cydopropanone. The simulation of (b) over tilde B-3(1) OXA reproduces the higher eBE portion of the spectrum very well. The term energy of the B-3(1) state is 0.883 +/- 0.012 eV. Photoelectron spectroscopic measurements have also been conducted for the other ion products of the O center dot- reaction with acetone. The photoelectron imaging spectrum of the acetylcarbene (AC) radical anion exhibits a broad, structureless feature, which is assigned to the (X) over tilde (3)A '' state of AC. The ground ((2)A '') and first excited ((2)A') states of the 1-methylvinoxy (1-MVO) radical have been observed in the photoelectron spectrum of the 1-MVO ion, and their vibronic structure has been analyzed.

Phosphorus-based functional groups as hydrogen bonding templates for rotaxane formation

We report on the use of the hydrogen bond acceptor properties of some phosphorus-containing functional groups for the assembly of a series of [2]rotaxanes. Phosphinamides, and the homologous thio– and selenophosphinamides, act as hydrogen bond acceptors that, in conjunction with an appropriately positioned amide group on the thread, direct the assembly of amide-based macrocycles around the axle to form rotaxanes in up to 60% yields. Employing solely phosphorus-based functional groups as the hydrogen bond accepting groups on the thread, a bis(phosphinamide) template and a phosphine oxide-phosphinamide template afforded the corresponding rotaxanes in 18 and 15 % yields, respectively. X-Ray crystallography of the rotaxanes shows the presence of up to four intercomponent hydrogen bonds between the amide groups of the macrocycle and various hydrogen bond accepting groups on the thread, including rare examples of amide-to-phosphonamide, -thiophosphinamide and -selenophosphinamide groups. With a phosphine oxide-phosphinamide thread, the solid state structure of the rotaxane is remarkable, featuring no direct intercomponent hydrogen bonds but rather a hydrogen bond network involving water molecules that bridge the H-bonding groups of the macrocycle and thread through bifurcated hydrogen bonds. The incorporation of phosphorus-based functional groups into rotaxanes may prove useful for the development of molecular shuttles in which the macrocycle can be used to hinder or expose binding ligating sites for metal-based catalysts.

Hydrolysis of triasulfuron, metsulfuron-methyl and chlorsulfuron in alkaline soil and aqueous solutions

The hydrolysis of triasulfuron, metsulfuron-methyl and chlorsulfuron in aqueous buffer solutions and in soil suspensions at pH values ranging from 5.2 to 11.2 was investigated. Hydrolysis of all three compounds in both aqueous buffer and soil suspensions was highly pH-sensitive. The rate of hydrolysis was much faster in the acidic pH range (5.2-6.2) than under neutral and moderately alkaline conditions (8.2-9.4), but it increased rapidly as the pH exceeded 10.2. All three compounds degraded faster at pH 5.2 than at pH 11.2. Hydrolysis rates of all three compounds could be described well with pseudo-first-order kinetics. There were no significant differences (P =0.05) in the rate constants (k, day-1) of the three compounds in soil suspensions from those in buffer solutions within the pH ranges studied. A functional relationship based on the propensity of nonionic and anionic species of the herbicides to hydrolyse was used to describe the dependence of the 'rate constant' on pH. The hydrolysis involving attack by neutral water was at least 100-fold faster when the sulfonylurea herbicides were undissociated (acidic conditions) than when they were present as the anion at near neutral pH. In aqueous buffer solution at pH > 11, a prominent degradation pathway involved O-demethylation of metsulfuron-methyl to yield a highly polar degradate, and hydrolytic opening of the triazine ring. It is concluded that these herbicides are not likely to degrade substantially through hydrolysis in most agricultural (C) 2000 Society of Chemical Industry.