Structural and kinetic studies of spin crossover in an Iron(II) complex with a novel tripodal ligand

Configurational and ligand conformational influences on the kinetics of (1)A(1) reversible arrow T-5(2) spin crossover in the Fe(II) complex with the novel tripodal ligand, 1,1,1-tris((N-(2-pyridylmethyl)-N-methylamino)methyl)ethane (tptMetame), have been explored. Despite having six chelate rings and three chiral nitrogen atoms, only one enantiomeric pair of isomers, Delta, SSS, and Lambda, RRR, of the complex ion is observed. The conformation of the three rings forming the upper ''cap'' of the complex structure can be assigned delta or lambda with respect to the 3-fold molecular axis. X-ray data at 300 and 153 K, above and below the critical temperature for the spin transition, show that the conformation of the ligand ''cap'' is the same as the absolute configuration of the complex, with the same Lambda lambda(CAP)(or Delta delta(CAP)) combination prevailing for both the LS ((1)A(1)) and HS (T-5(2)) isomers. Molecular mechanics calculations further show that the ligand energy remains lowest for this Lambda lambda(CAP) (or Delta delta(CAP)) combination at all Fe-N distances over the range spanning the LS and HS isomers. Measurements of the spin crossover relaxation time have been carried out in solution over the temperature range 293-170 K. The observed monophasic relaxation traces are also consistent with the absolute configuration of the complex remaining unaltered during the spin crossover.

Liquid-liquid slug flow: Hydrodynamics and pressure drop

In this paper, the hydrodynamics and the pressure drop of liquid-liquid slug flow in round microcapillaries are presented. Two liquid-liquid flow systems are considered, viz. water-toluene and ethylene glycol/water-toluene. The slug lengths of the alternating continuous and dispersed phases were measured as a function of the slug velocity (0.03-0.5 m/s), the organic-to-aqueous flow ratio (0.1-4.0), and the microcapillary internal diameter (248 and 498 mu m). The pressure drop is modeled as the sum of two contributions: the frictional and the interface pressure drop. Two models are presented, viz, the stagnant film model and the moving film model. Both models account for the presence of a thin liquid film between the dispersed phase slug and the capillary wall. It is found that the film velocity is of negligible influence on the pressure drop. Therefore, the stagnant film model is adequate to accurately predict the liquid-liquid slug flow pressure drop. The influence of inertia and the consequent change of the slug cap curvature are accounted for by modifying Bretherton's curvature parameter in the interface pressure drop equation. The stagnant film model is in good agreement with experimental data with a mean relative error of less than 7%.

Constitutive and Treatment-Induced CXCL8-Signalling Selectively Modulates the Efficacy of Anti-Metabolite Therapeutics in Metastatic Prostate Cancer

Background: The current study was undertaken to characterize the effect of anti-metabolites on inducing CXCL8 signaling and determining whether the constitutive and/or drug-induced CXCL8 signaling in metastatic prostate cancer (CaP) cells modulates their sensitivity to this class of agent.

Methods: The response of metastatic CaP cells to 5-Fluorouracil (5-FU), Pemetrexed or Tomudex was determined using cell count assays, flow cytometry and PARP cleavage analysis. Quantitative-PCR, ELISA and immunoblots were employed to determine effects of drugs or CXCL8 administration on target gene/protein expression.

Results: Administration of 5-FU but not pemetrexed potentiated CXCL8 secretion and increased CXCR1 and CXCR2 gene expression in metastatic PC3 cells. Consistent with this, the inhibition of CXCL8 signaling using a CXCR2 antagonist, AZ10397767, increased the cytotoxicity of 5-FU by 4-fold (P,0.001), and increased 5-FU-induced apoptosis in PC3 cells (P,0.01). In contrast, while administration of AZ10397767 had no effect on the sensitivity of pemetrexed, the CXCR2 antagonist exerted the greatest effect in increasing the sensitivity of PC3 cells to Tomudex, a directed thymidylate synthase (TS) inhibitor. Subsequent experiments confirmed that administration of recombinant human CXCL8 increased TS expression, a response mediated in part by the CXCR2 receptor. Moreover, siRNA-mediated knockdown of the CXCL8-target gene Bcl-2 increased the sensitivity of PC3 cells to 5-FU.

Conclusions: CXCL8 signaling provides a selective resistance of metastatic prostate cancer cells to specific anti-metabolites by promoting a target-associated resistance, in addition to underpinning an evasion of treatment-induced apoptosis. © 2012 Wilson et al.

Gender mainstreaming and the Common Agricultural Policy

While there are many case studies looking at gender mainstreaming in national contexts, this article offers a pan-European perspective to examine how a stated commitment to gender equality at this meta-level works in practice. The European Union’s (EU) stated commitment to gender mainstreaming the Common Agricultural Policy (CAP) is critically reviewed. The article reviews theoretical literature on gender mainstreaming, considers the position of women in agriculture across Europe, and examines efforts by the EU to gender mainstream the CAP. It argues that at best, gender mainstreaming focuses on the symptoms of gender inequality in agriculture rather than the causes. Because of this, gender mainstreaming cannot be transformative in this context. Little thought has been given to the practical difficulties of actually gender mainstreaming a policy such as the CAP. The EU’s priority for the CAP focuses on the mainstream business goal of a viable agricultural industry and does not pay any heed to gender inequalities in agriculture. In short, the stated commitment to gender mainstreaming is empty rhetoric

Development of calcium phosphate cement for the augmentation of traumatically fractured porcine specimens using vertebroplasty

The study aim was to develop and apply an experimental technique to determine the biomechanical effect of polymethylmethacrylate (PMMA) and calcium phosphate (CaP) cement on the stiffness and strength of augmented vertebrae following traumatic fracture. Twelve burst type fractures were generated in porcine three-vertebra segments. The specimens were randomly split into two groups (n=6), imaged using microCT and tested under axial loading. The two groups of fractured specimens underwent a vertebroplasty procedure, one group was augmented with CaP cement designed and developed at Queen's University Belfast. The other group was augmented with PMMA cement (WHW Plastics, Hull, UK). The specimens were imaged and re-tested . An intact single vertebra specimen group (n=12) was also imaged and tested under axial loading. A significant decrease (p<0.01) was found between the stiffness of the fractured and intact groups, demonstrating that the fractures generated were sufficiently severe, to adversely affect mechanical behaviour. Significant increase (p<0.01) in failure load was found for the specimen group augmented with the PMMA cement compared to the pre-augmentation group, conversely, no significant increase (p<0.01) was found in the failure load of the specimens augmented with CaP cement, this is attributed to the significantly (p<0.05) lower volume of CaP cement that was successfully injected into the fracture, compared to the PMMA cement. The effect of the percentage of cement fracture fill, cement modulus on the specimen stiffness and ultimate failure load could be investigated further by using the methods developed within this study to test a more injectable CaP cement.

Survival without disability to age 5 years after neonatal caffeine therapy for apnea of prematurity

Very preterm infants are prone to apnea and have an increased risk of death or disability. Caffeine therapy for apnea of prematurity reduces the rates of cerebral palsy and cognitive delay at 18 months of age.

Climate Change Mitigation and Intergenerational Justice

Existing climate change mitigation policies are particularly concerned with the reconciliation of two seemingly conflicting aims: environmental protection and economic efficiency. The normative principles underlying these policies meanwhile focus on two central ideas: fair burden-sharing and agents' responsibility. However, both existing policy instruments and their supporting philosophical principles are highly problematic in terms of intergenerational justice and truly effective climate change mitigation. Three competing conceptions for allocating and distributing the burdens of climate change mitigation (cap-and-trade schemes, carbon emission taxes, and personal ecological space quotas) and their compatibility with principles of intra- and intergenerational justice are analysed and evaluated. None of the proposed instruments is able to satisfy the demands of effective mitigation and egalitarian justice on its own, which suggests that existing proposals for the distribution of emission rights and climate change-related costs need to be supported by a thicker account of intergenerational justice.

A sparse representation based fast detection method for surface defect detection of bottle caps

A practical machine-vision-based system is developed for fast detection of defects occurring on the surface of bottle caps. This system can be used to extract the circular region as the region of interests (ROI) from the surface of a bottle cap, and then use the circular region projection histogram (CRPH) as the matching features. We establish two dictionaries for the template and possible defect, respectively. Due to the requirements of high-speed production as well as detecting quality, a fast algorithm based on a sparse representation is proposed to speed up the searching. In the sparse representation, non-zero elements in the sparse factors indicate the defect's size and position. Experimental results in industrial trials show that the proposed method outperforms the orientation code method (OCM) and is able to produce promising results for detecting defects on the surface of bottle caps.

Experimental and Computational Approach Investigating Burst Fracture Augmentation Using PMMA and Calcium Phosphate Cements

The aim of the study was to use a computational and experimental approach to evaluate, compare and predict the ability of calcium phosphate (CaP) and poly (methyl methacrylate) (PMMA) augmentation cements to restore mechanical stability to traumatically fractured vertebrae, following a vertebroplasty procedure. Traumatic fractures (n = 17) were generated in a series of porcine vertebrae using a drop-weight method. The fractured vertebrae were imaged using μCT and tested under axial compression. Twelve of the fractured vertebrae were randomly selected to undergo a vertebroplasty procedure using either a PMMA (n = 6) or a CaP cement variation (n = 6). The specimens were imaged using μCT and re-tested. Finite element models of the fractured and augmented vertebrae were generated from the μCT data and used to compare the effect of fracture void fill with augmented specimen stiffness. Significant increases (p <0.05) in failure load were found for both of the augmented specimen groups compared to the fractured group. The experimental and computational results indicated that neither the CaP cement nor PMMA cement could completely restore the vertebral mechanical behavior to the intact level. The effectiveness of the procedure appeared to be more influenced by the volume of fracture filled rather than by the mechanical properties of the cement itself.

Power-Capped DVFS and Thread Allocation with ANN Models on Modern NUMA Systems

Abstract—Power capping is an essential function for efficient power budgeting and cost management on modern server systems. Contemporary server processors operate under power caps by using dynamic voltage and frequency scaling (DVFS). However, these processors are often deployed in non-uniform memory
access (NUMA) architectures, where thread allocation between cores may significantly affect performance and power consumption. This paper proposes a method which maximizes performance under power caps on NUMA systems by dynamically optimizing two knobs: DVFS and thread allocation. The method selects the optimal combination of the two knobs with models based on artificial neural network (ANN) that captures the nonlinear effect of thread allocation on performance. We implement
the proposed method as a runtime system and evaluate it with twelve multithreaded benchmarks on a real AMD Opteron based NUMA system. The evaluation results show that our method outperforms a naive technique optimizing only DVFS by up to
67.1%, under a power cap.

Coexistence of GMOs in the EU – A Veritable Choice?

This chapter examines the issue of coexistence of genetically modified organisms (GMOs) alongside conventional and organic crops. The central focus is on whether there is a veritable opportunity for coexistence of all three types of crops, which allows for freedom of choice by both farmers and consumers. It commences by considering the nature of the general GM regime, the relationship between the frameworks for cultivation and the use and sale of GM food and feed, and the main elements of the cultivation regime. In light of this, the concept of coexistence is considered, with an evaluation of both the legal and practical elements. Although the general GM regime is controlled at an EU level, coexistence is apparently left to the Member States who may take appropriate coexistence measures. Nonetheless, the Commission has created Recommendations that are to guide the Member States in their choice of measures. To a great extent, what is considered ‘appropriate’ is to be determined by the economic impact upon the farmers and the relationship with the labelling thresholds. The chapter evaluates the future of coexistence, bearing in mind the continued use of the safeguard clauses, the declaration of ‘GM-free’ regions, the potential for national ‘opt-outs’ and the general practical challenges of maintaining coexistence including the ‘domino effect’. Overall, it is arguable that coexistence is a misnomer and that if the term’s meaning is strictly maintained then veritable coexistence that allows for freedom of choice by both farmers and consumers seems unattainable. Although not directly controlled by CAP, there are strong areas of overlap and they share a number of similar objectives; the chapter will conclude by considering whether the approaches in relation to CAP and the cultivation of GMOs are converging or diverging.

Improving Bandwidth Efficiency in E-band Communication Systems

The allocation of a large amount of bandwidth by regulating bodies in the 70/80 GHz band, i.e., the E-band, has opened up new potentials and challenges for providing affordable and reliable Gigabit per second wireless point-to-point links. This article first reviews the available bandwidth and licensing regulations in the E-band. Subsequently, different propagation models, e.g., the ITU-R and Cane models, are compared against measurement results and it is concluded that to meet specific availability requirements, E-band wireless systems may need to be designed with larger fade margins compared to microwave systems. A similar comparison is carried out between measurements and models for oscillator phase noise. It is confirmed that phase noise characteristics, that are neglected by the models used for narrowband systems, need to be taken into account for the wideband systems deployed in the E-band. Next, a new multi-input multi-output (MIMO) transceiver design, termed continuous aperture phased (CAP)-MIMO, is presented. Simulations show that CAP-MIMO enables E-band systems to achieve fiber-optic like throughputs. Finally, it is argued that full-duplex relaying can be used to greatly enhance the coverage of E-band systems without sacrificing throughput, thus, facilitating their application in establishing the backhaul of heterogeneous networks.