Segmental relaxation in semicrystalline polymers: a mean field model for the distribution of relaxation times in confined regimes

The effect of confinement in the segmental relaxation of polymers is considered. On the basis of a thermodynamic model we discuss the emerging relevance of the fast degrees of freedom in stimulating the much slower segmental relaxation, as an effect of the constraints at the walls of the amorphous regions. In the case that confinement is due to the presence of crystalline domains, a quasi-poissonian distribution of local constraining conditions is derived as a result of thermodynamic equilibrium. This implies that the average free energy barrier $\Delta F$ for conformational rearrangement is of the same order of the dispersion of the barrier heights, $\delta (\Delta F)$, around $\Delta F$. As an example, we apply the results to the analysis of the $\alpha$-relaxation as observed by dielectric broad band spectroscopy in semicrystalline poly(ethylene terephthalate) cold-crystallized from either an isotropic or an oriented glass. It is found that in the latter case the regions of cooperative rearrangement are significantly larger than in the former.Comment: 10 pages, 4 figures .ep

Differential associations of conduct disorder, callous‑unemotional traits and irritability with outcome expectations and values regarding the consequences of aggression

Background: Previous work has examined the association of aggression levels and callous-unemotional traits with outcome expectations and values regarding the consequences of aggression. Less work has examined the outcome expectations and values regarding the consequences of aggression of adolescents with Conduct Disorder (CD). Also, no studies have examined links between irritability (a second socio-affective trait associated with CD) and these social cognitive processes despite the core function of anger in retaliatory aggression and establishing dominance. Method: The current study, investigating these issues, involved 193 adolescents (typically developing [TD; N = 106], 87 cases with CD [N = 87]). Participants completed an adaptation of the Outcomes Expectations and Values Questionnaire and were assessed for CU traits and irritability via the Inventory of Callous-Unemotional traits and the Affective Reactivity Index. Results: While CD was associated with atypical outcome expectations this was not seen within statistical models including CU traits and irritability. CU traits were associated with decreased expectation that aggression would result in feelings of remorse and victim suffering, as well as decreased concern that aggressive acts would result in punishment and victim suffering. Irritability was associated with increased expectations and concern that aggression would result in dominance and forced respect. Conclusions: The results suggest that CU traits and irritability, often present in youth with CD, are associated with different forms of maladaptive outcome expectations and values regarding the consequences of aggression. This suggests that the atypical social cognitive processes underlying aggressive behavior among youth exhibiting CU traits may differ from those exhibiting problems regulating anger

Driving factors of a vegetation shift from Scots pine to pubescent oak in dry Alpine forests

An increasing number of studies have reported on forest declines and vegetation shifts triggered by drought. In the Swiss Rhone valley (Valais), one of the driest inner-Alpine regions, the species composition in low elevation forests is changing: The sub-boreal Scots pine (Pinus sylvestris L.) dominating the dry forests is showing high mortality rates. Concurrently the sub-Mediterranean pubescent oak (Quercus pubescens Willd.) has locally increased in abundance. However, it remains unclear whether this local change in species composition is part of a larger-scale vegetation shift. To study variability in mortality and regeneration in these dry forests we analysed data from the Swiss national forest inventory (NFI) on a regular grid between 1983 and 2003, and combined it with annual mortality data from a monitoring site. Pine mortality was found to be highest at low elevation (below 1000 m a.s.l.). Annual variation in pine mortality was correlated with a drought index computed for the summer months prior to observed tree death. A generalized linear mixed-effects model indicated for the NFI data increased pine mortality on dryer sites with high stand competition, particularly for small-diameter trees. Pine regeneration was low in comparison to its occurrence in the overstorey, whereas oak regeneration was comparably abundant. Although both species regenerated well at dry sites, pine regeneration was favoured at cooler sites at higher altitude and oak regeneration was more frequent at warmer sites, indicating a higher adaptation potential of oaks under future warming. Our results thus suggest that an extended shift in species composition is actually occurring in the pine forests in the Valais. The main driving factors are found to be climatic variability, particularly drought, and variability in stand structure and topography. Thus, pine forests at low elevations are developing into oak forests with unknown consequences for these ecosystems and their goods and services

On the Exploitation of a High-throughput SHA-256 FPGA Design for HMAC

High-throughput and area-efficient designs of hash functions and corresponding mechanisms for Message Authentication Codes (MACs) are in high demand due to new security protocols that have arisen and call for security services in every transmitted data packet. For instance, IPv6 incorporates the IPSec protocol for secure data transmission. However, the IPSec's performance bottleneck is the HMAC mechanism which is responsible for authenticating the transmitted data. HMAC's performance bottleneck in its turn is the underlying hash function. In this article a high-throughput and small-size SHA-256 hash function FPGA design and the corresponding HMAC FPGA design is presented. Advanced optimization techniques have been deployed leading to a SHA-256 hashing core which performs more than 30% better, compared to the next better design. This improvement is achieved both in terms of throughput as well as in terms of throughput/area cost factor. It is the first reported SHA-256 hashing core that exceeds 11Gbps (after place and route in Xilinx Virtex 6 board)

Systematic Construction of Nonlinear Product Attacks on Block Ciphers

A major open problem in block cipher cryptanalysis is discovery of new invariant properties of complex type. Recent papers show that this can be achieved for SCREAM, Midori64, MANTIS-4, T-310 or for DES with modified S-boxes. Until now such attacks are hard to find and seem to happen by some sort of incredible coincidence. In this paper we abstract the attack from any particular block cipher. We study these attacks in terms of transformations on multivariate polynomials. We shall demonstrate how numerous variables including key variables may sometimes be eliminated and at the end two very complex Boolean polynomials will become equal. We present a general construction of an attack where multiply all the polynomials lying on one or several cycles. Then under suitable conditions the non-linear functions involved will be eliminated totally. We obtain a periodic invariant property holding for any number of rounds. A major difficulty with invariant attacks is that they typically work only for some keys. In T-310 our attack works for any key and also in spite of the presence of round constants

Some Results on the Known Classes of Quadratic APN Functions

In this paper, we determine the Walsh spectra of three classes of quadratic APN functions and we prove that the class of quadratic trinomial APN functions constructed by Gölo\u glu is affine equivalent to Gold functions

Practical free-start collision attacks on 76-step SHA-1

In this paper we analyze the security of the compression function of SHA-1 against collision attacks, or equivalently free-start collisions on the hash function. While a lot of work has been dedicated to the analysis of SHA-1 in the past decade, this is the first time that free-start collisions have been considered for this function. We exploit the additional freedom provided by this model by using a new start-from-the-middle approach in combination with improvements on the cryptanalysis tools that have been developed for SHA-1 in the recent years. This results in particular in better differential paths than the ones used for hash function collisions so far. Overall, our attack requires about $2^{50}$ evaluations of the compression function in order to compute a one-block free-start collision for a 76-step reduced version, which is so far the highest number of steps reached for a collision on the SHA-1 compression function. We have developed an efficient GPU framework for the highly branching code typical of a cryptanalytic collision attack and used it in an optimized implementation of our attack on recent GTX 970 GPUs. We report that a single cheap US\$ 350 GTX 970 is sufficient to find the collision in less than 5 days. This showcases how recent mainstream GPUs seem to be a good platform for expensive and even highly-branching cryptanalysis computations. Finally, our work should be taken as a reminder that cryptanalysis on SHA-1 continues to improve. This is yet another proof that the industry should quickly move away from using this function

Candida albicans-produced farnesol stimulates Pseudomonas quinolone signal production in LasR-defective Pseudomonas aeruginosa strains

Candida albicans has been previously shown to stimulate the production of Pseudomonas aeruginosa phenazine toxins in dual-species colony biofilms. Here, we report that P. aeruginosa lasR mutants, which lack the master quorum sensing system regulator, regain the ability to produce quorum-sensing-regulated phenazines when cultured with C. albicans. Farnesol, a signalling molecule produced by C. albicans, was sufficient to stimulate phenazine production in LasR− laboratory strains and clinical isolates. P. aeruginosa ΔlasR mutants are defective in production of the Pseudomonas quinolone signal (PQS) due to their inability to properly induce pqsH, which encodes the enzyme necessary for the last step in PQS biosynthesis. We show that expression of pqsH in a ΔlasR strain was sufficient to restore PQS production, and that farnesol restored pqsH expression in ΔlasR mutants. The farnesol-mediated increase in pqsH required RhlR, a transcriptional regulator downstream of LasR, and farnesol led to higher levels of N-butyryl-homoserine lactone, the small molecule activator of RhlR. Farnesol promotes the production of reactive oxygen species (ROS) in a variety of species. Because the antioxidant N-acetylcysteine suppressed farnesol-induced RhlR activity in LasR− strains, and hydrogen peroxide was sufficient to restore PQS production in las mutants, we propose that ROS are responsible for the activation of downstream portions of this quorum sensing pathway. LasR mutants frequently arise in the lungs of patients chronically infected with P. aeruginosa. The finding that C. albicans, farnesol or ROS stimulate virulence factor production in lasR strains provides new insight into the virulence potential of these strains