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.

Hip and knee kinematics display complex and time-varying sagittal kinematics during repetitive stepping: Implications for design of a functional fatigue model of the knee extensors and flexors

The validity of fatigue protocols involving multi-joint movements, such as stepping, has yet to be clearly defined. Although surface electromyography can monitor the fatigue state of individual muscles, the effects of joint angle and velocity variation on signal parameters are well established. Therefore, the aims of this study were to i) describe sagittal hip and knee kinematics during repetitive stepping ii) identify periods of high inter-trial variability and iii) determine within-test reliability of hip and knee kinematic profiles. A group of healthy men (N = 15) ascended and descended from a knee-high platform wearing a weighted vest (10%BW) for 50 consecutive trials. The hip and knee underwent rapid flexion and extension during step ascent and descent. Variability of hip and knee velocity peaked between 20-40% of the ascent phase and 80-100% of the descent. Significant (p<0.05) reductions in joint range of motion and peak velocity during step ascent were observed, while peak flexion velocity increased during descent. Healthy individuals use complex hip and knee motion to negotiate a knee-high step with kinematic patterns varying across multiple repetitions. These findings have important implications for future studies intending to use repetitive stepping as a fatigue model for the knee extensors and flexors.

Multi-utility finance : a problematic case

This paper treats one particular version of the multi-utility strategy as experienced by the Hyder Group. We examine some aspectw of the company's financial performance and consider the implications.

Basic finance made accessible in Excel 2007 : "the big 5, plus 2"

The basic principles and equations are developed for elementary finance, based on the concept of compound interest. The five quantities of interest in such problems are present value, future value, amount of periodic payment, number of periods and the rate of interest per period. We consider three distinct means of computing each of these five quantities in Excel 2007: (i) use of algebraic equations, (ii) by recursive schedule and the Goal Seek facility, and (iii) use of Excel's intrinsic financial functions. The paper is intended to be used as the basis for a lesson plan and contains many examples and solved problems. Comment is made regarding the relative difficulty of each approach, and a prominent theme is the systematic use of more than one method to increase student understanding and build confidence in the answer obtained. Full instructions to build each type of model are given and a complete set of examples and solutions may be downloaded (Examples.xlsx and Solutions.xlsx).

Teaching basic finance with Excel, and without pain

The five quantities of interest in elementary finance problems are present value, future value, amount of periodic payment, number of periods and the rate of compound interest per period. A recursive approach to computing each of these five quantities in a modern version of Excel, for the case of ordinary annuities, is described. The aim is to increase student understanding and build confidence in the answer obtained, and this may be achieved with only linear relationships and in cases where student knowledge of algebra is essentially zero. Annuity problems may be solved without use of logarithms and black-box intrinsic functions; these being used only as check mechanisms. The author has had success with the method at Bond University and surrounding high schools in Queensland, Australia.

Plasma break-down and re-build : same functional vertical graphenes from diverse natural precursors

Plasmas, the 4th state of matter, uniformly transform natural precursors with different chemical composition in solid, liquid, and gas states into the same functional vertical graphenes in a single-step process within a few minutes. Functional vertical graphenes show reliable biosensing properties, strong binding with proteins, and improved adhesion to substrates.

Functional impairments characterising mild, moderate and severe hallux valgus

Objective Hallux valgus has been linked to functional disability and increased falls risk, but mechanisms underpinning functional disability are unclear. This study investigated functional performance, muscle strength and plantar pressures in adults with mild, moderate, and severe HV compared to controls, while considering the influence of foot pain. Methods Sixty adults with hallux valgus (classified as mild, moderate and severe on dorsalplantar radiographs) and 30 controls participated. Measures included: hallux plantarflexion and abduction strength, walking performance, postural sway and forefoot plantar pressures. Multiple analysis of covariance and pairwise comparisons (p<0.05, Bonferroni adjustment) were used to investigate differences between groups, adjusting for age, sex, body mass index and foot pain. Results Hallux plantarflexion and abduction strength was significantly reduced in those with moderate (mean differences: plantarflexion -45.8N, abduction -12.3N, p<0.001) and severe hallux valgus (plantarflexion -50.1N, p<0.001; abduction -11.2N, p=0.01) compared to controls. A significant reduction in hallux peak pressure and pressure-time integral was evident in moderate (peak pressure -90.8kPa, p<0.001) and severe hallux valgus (peak pressure -106.2kPa, p<0.001) compared to controls. Those with severe hallux valgus also demonstrated increased mediolateral postural sway in single leg stance compared to controls (3.5cm, p=0.01). Conclusion Moderate to severe hallux valgus is associated with reduced hallux plantar pressures and strength measures, while relatively normal function compared to controls was found in those with mild deformity. Greater understanding of specific functional deficits associated with different stages of hallux valgus will help inform clinical management and future research.

Synthesis of functional nanoassemblies in reactive plasmas

Synthesis of various functional nanoassemblies, by using a combination of low-pressure reactive plasma-enhanced chemical deposition and plasma-assisted rf magnetron sputtering deposition is reported. This paper details how selective generation and manipulation of the required building blocks and management of unwanted nanoparticle contaminants, can be used for plasma-aided nanofabrication of carbon nanotip microemitter structures, ultra-high aspect ratio semiconductor nanowires, ordered quantum dot arrays, and microporous hydroxyapatite bioceramics. Emerging challenges of the plasma-aided synthesis of functional nanofilms and nanoassemblies are also discussed.

Integrated plasma-aided nanofabrication facility: Operation, parameters, and assembly of quantum structures and functional nanomaterials

The development, operation, and applications of two configurations of an integrated plasma-aided nanofabrication facility (IPANF) comprising low-frequency inductively coupled plasma-assisted, low-pressure, multiple-target RF magnetron sputtering plasma source, are reported. The two configurations of the plasma source have different arrangements of the RF inductive coil: a conventional external flat spiral "pancake" coil and an in-house developed internal antenna comprising two orthogonal RF current sheets. The internal antenna configuration generates a "unidirectional" RF current that deeply penetrates into the plasma bulk and results in an excellent uniformity of the plasma over large areas and volumes. The IPANF has been employed for various applications, including low-temperature plasma-enhanced chemical vapor deposition of vertically aligned single-crystalline carbon nanotips, growth of ultra-high aspect ratio semiconductor nanowires, assembly of optoelectronically important Si, SiC, and Al1-xInxN quantum dots, and plasma-based synthesis of bioactive hydroxyapatite for orthopedic implants.

Ion-assisted functional monolayer coating of nanorod arrays in hydrogen plasmas

Uniformity of postprocessing of large-area, dense nanostructure arrays is currently one of the greatest challenges in nanoscience and nanofabrication. One of the major issues is to achieve a high level of control in specie fluxes to specific surface areas of the nanostructures. As suggested by the numerical experiments in this work, this goal can be achieved by manipulating microscopic ion fluxes by varying the plasma sheath and nanorod array parameters. The dynamics of ion-assisted deposition of functional monolayer coatings onto two-dimensional carbon nanorod arrays in a hydrogen plasma is simulated by using a multiscale hybrid numerical simulation. The numerical results show evidence of a strong correlation between the aspect ratios and nanopattern positioning of the nanorods, plasma sheath width, and densities and distributions of microscopic ion fluxes. When the spacing between the nanorods and/or their aspect ratios are larger, and/or the plasma sheath is wider, the density of microscopic ion current flowing to each of the individual nanorods increases, thus reducing the time required to apply a functional monolayer coating down to 11 s for a 7-μm-wide sheath, and to 5 s for a 50-μm-wide sheath. The computed monolayer coating development time is consistent with previous experimental reports on plasma-assisted functionalization of related carbon nanostructures [B. N. Khare et al., Appl. Phys. Lett. 81, 5237 (2002)]. The results are generic in that they can be applied to a broader range of plasma-based processes and nanostructures, and contribute to the development of deterministic strategies of postprocessing and functionalization of various nanoarrays for nanoelectronic, biomedical, and other emerging applications.

Brain decoding based on functional magnetic resonance imaging using machine learning : a comparative study

Brain decoding of functional Magnetic Resonance Imaging data is a pattern analysis task that links brain activity patterns to the experimental conditions. Classifiers predict the neural states from the spatial and temporal pattern of brain activity extracted from multiple voxels in the functional images in a certain period of time. The prediction results offer insight into the nature of neural representations and cognitive mechanisms and the classification accuracy determines our confidence in understanding the relationship between brain activity and stimuli. In this paper, we compared the efficacy of three machine learning algorithms: neural network, support vector machines, and conditional random field to decode the visual stimuli or neural cognitive states from functional Magnetic Resonance data. Leave-one-out cross validation was performed to quantify the generalization accuracy of each algorithm on unseen data. The results indicated support vector machine and conditional random field have comparable performance and the potential of the latter is worthy of further investigation.

Anterior temporal cortex and semantic memory : reconciling findings from neuropsychology and functional imaging

Studies of semantic impairment arising from brain disease suggest that the anterior temporal lobes are critical for semantic abilities in humans; yet activation of these regions is rarely reported in functional imaging studies of healthy controls performing semantic tasks. Here, we combined neuropsychological and PET functional imaging data to show that when healthy subjects identify concepts at a specific level, the regions activated correspond to the site of maximal atrophy in patients with relatively pure semantic impairment. The stimuli were color photographs of common animals or vehicles, and the task was category verification at specific (e.g., robin), intermediate (e.g., bird), or general (e.g., animal) levels. Specific, relative to general, categorization activated the antero-lateral temporal cortices bilaterally, despite matching of these experimental conditions for difficulty. Critically, in patients with atrophy in precisely these areas, the most pronounced deficit was in the retrieval of specific semantic information.

Comparison of block and event-related experimental designs in diffusion-weighted functional MRI

PURPOSE To compare diffusion-weighted functional magnetic resonance imaging (DfMRI), a novel alternative to the blood oxygenation level-dependent (BOLD) contrast, in a functional MRI experiment. MATERIALS AND METHODS Nine participants viewed contrast reversing (7.5 Hz) black-and-white checkerboard stimuli using block and event-related paradigms. DfMRI (b = 1800 mm/s2 ) and BOLD sequences were acquired. Four parameters describing the observed signal were assessed: percent signal change, spatial extent of the activation, the Euclidean distance between peak voxel locations, and the time-to-peak of the best fitting impulse response for different paradigms and sequences. RESULTS The BOLD conditions showed a higher percent signal change relative to DfMRI; however, event-related DfMRI showed the strongest group activation (t = 21.23, P < 0.0005). Activation was more diffuse and spatially closer to the BOLD response for DfMRI when the block design was used. DfMRIevent showed the shortest TTP (4.4 +/- 0.88 sec). CONCLUSION The hemodynamic contribution to DfMRI may increase with the use of block designs.

Examining the role of within functional area resource–capability complementarity in achieving customer and product-based performance outcomes

Adopting both the resource-based view and dynamic capability theory this study advances the contention that firms must possess both resources and capabilities at a superior level to achieve superior customer and product performance. To examine this contention this study investigates the individual effect of the complementarity between marketing resources and capability and complementarity between innovation resources and capability on customer and product performance respectively. The results of a survey of 171 B2B manufacturing firms show a significant main effect for complementarity between marketing resources–capability and complementarity between innovation resources–capability on customer and product performance. The findings also show that complementarity marketing resources–capability has a stronger positive relationship with customer performance than with product performance, while complementarity between innovation resources–capability has a stronger positive relationship with product performance than with customer performance.

Public Finance for REDD+ in Kenya

Kenya aims to prepare for both public and private Reduced Emission from Deforestation and Degradation (REDD+) investment flows. This chapter examines how current Kenyan law can be used as a starting point for building a regulatory regime to support public sector finance. For present purposes, ‘public sector finance’ is defined as money flowing from multilateral international institutions and bi-lateral donor funds. Key issues addressed by this chapter • The nature and form of public sector finance for REDD+ in Kenya. • The management and laws relating to public funds in Kenya; • Mechanisms that can be utilised to manage risk associated with REDD+ investments with a focus on Kenyan anti-corruption laws and policies; • The regulatory regime for distributing the benefits from REDD+ investment to relevant forest stakeholders.