Photochemical, photophysical and redox properties of novel fulgimide derivatives with attached 2,2 '-bipyridine (bpy) and [M(bpy)(3)](2+) (M = Ru and Os) moieties

Fulgimides monosubstituted with [M(bpy)(3)](2+) (M = Ru, Os; bpy = 2,2'-bipyridine) chromophore units and with a single bpy group were synthesized and investigated as components of conceivable dinuclear photochromic switches of luminescence. The E-, Z- and closed-ring (C) photoisomer forms of the bpy-bound fulgimide were successfully separated by semi-preparative HPLC. The same procedure failed, however, in the case of the [M(bpy)(3)](2+)-substituted fulgimides. Energy transfer from the excited photochromic unit to the metal-bpy centre competes with the fulgimide cyclization, reducing the photocyclization quantum yields by approximately one order of magnitude compared to the non-complexed fulgimide-bpy ligand (phi(EC) = 0.17, phi(EZ) = 0.071, phi(ZE) = 0.15 at lambda(exc) = 334 nm). The cycloreversion of the fulgimide-bpy ligand is less efficient (phi(CE) = 0.047 at lambda(exc) = 520 nm). The intensity of the (MLCT)-M-3-based luminescence of the metal-bpy chromophore (in MeCN, phi(deaer) = 6.6 x 10(-2) and tau(deaer) = 1.09 mu s for Ru; phi(deaer) = 6.7 x 10(-3) and tau(deaer) = 62 ns for Os) is not affected by the fulgimide photoconversion. These results and supporting spectro-electrochemical data reveal that the lowest triplet excited states of the photochromic fulgimide moiety in all its E-, Z- and closed-ring forms lie above the lowest 3MLCT levels of the attached ruthenium and osmium chromophores. The actual components are therefore unlikely to form a triad acting as functional switch of energy transfer from [Ru(bpy)(3)](2+) to [Os(bpy)(3)](2+) through the photochromic fulgimide bridge.

Peptide mediated formation of hierarchically organized solution and solid state polymer nanostructures

Biologically-inspired peptide sequences have been explored as auxiliaries to mediate self-assembly of synthetic macromolecules into hierarchically organized solution and solid state nanostructures. Peptide sequences inspired by the coiled coil motif and "switch" peptides, which can adopt both amphiphilic alpha-helical and beta-strand conformations, were conjugated to poly(ethylene glycol) (PEG). The solution and solid state self-assembly of these materials was investigated using a variety of spectroscopic, scattering and microscopic techniques. These experiments revealed that the folding and organization properties of the peptide sequences are retained upon conjugation of PEG and that they provide the driving force for the formation of the different nanoscale structures which were observed. The possibility of using defined peptide sequences to direct structure formation of synthetic polymers together with the potential of peptide sequences to induce a specific biological response offers interesting prospects for the development of novel self-assembled and biologically active materials.

EOQ, JIT and fixed costs in the Ready-mixed concrete industry

The successful implementation of just-in-time (JIT) purchasing policy in many industries has prompted many companies that still use the economic order quantity (EOQ) purchasing policy to ponder if they should switch to the JIT purchasing policy. Despite existing studies that directly compare the costs between the EOQ and JIT purchasing systems, this decision is, however, still difficult to be made, especially when price discount has to be considered. JIT purchasing may not always be successful even though plants that adopted JIT operations have experienced or can take advantage of physical space reduction. Hence, the objective of this study is to expand on a classical EOQ with a price discount model to derive the EOQ–JIT cost indifference point. The objective was tested and achieved through a survey and case study conducted in the ready-mixed concrete industry in Singapore.

Probing the receptor interactions of an H5 avian influenza virus using a baculovirus expression system and functionalised poly(acrylic acid) ligands

Influenza viruses attach to host cells by binding to terminal sialic acid (Neu5Ac) on glycoproteins or glycolipids. Both the linkage of Neu5Ac and the identity of other carbohydrates within the oligosaccharide are thought to play roles in restricting the host range of the virus. In this study, the receptor specificity of an H5 avian influenza virus haemagglutinin protein that has recently infected man (influenza strain A/Vietnam/1194/04) has been probed using carbohydrate functionalised poly(acrylic acid) polymers. A baculovirus expression system that allows facile and safe analysis of the Neu5Ac binding specificity of mutants of H5 HA engineered at sites that are predicted to effect a switch in host range has also been developed. (C) 2007 Elsevier Ltd. All rights reserved.

A new strategy for the blind MMSE equalization

This paper describes a new strategy for the blind equalization so that the blind Constant Module Algorithm (CMA) can be smoothly switched to the decision- directed (DD) equalization. First, we propose a combination approach by running the CMA and DD equalization simultaneously to obtain a smooth switch between them. We then describe an "anchoring process" to eliminate the effect from the CMA at the steady state to achieve low residual noise. The overall equalization can be regarded as the DD equalization being anchored by the combination approach. Numerical simulations are given to verify the proposed strategy.

An improved distributed dynamic channel assignment scheme for dense WLANs

The popularity of wireless local area networks (WLANs) has resulted in their dense deployment in many cities around the world. The increased interference among different WLANs severely degrades the throughput achievable. This problem has been further exacerbated by the limited number of frequency channels available. An improved distributed and dynamic channel assignment scheme that is simple to implement and does not depend on the knowledge of the throughput function is proposed in this work. It also allows each access point (AP) to asynchronously switch to the new best channel. Simulation results show that our proposed scheme converges much faster than similar previously reported work, with a reduction in convergence time and channel switches as much as 77.3% and 52.3% respectively. When it is employed in dynamic environments, the throughput improves by up to 12.7%.

Performance and conformance results of the deterministic DVB-T equalizer

One of the enablers for new consumer electronics based products to be accepted in to the market is the availability of inexpensive, flexible and multi-standard chipsets and services. DVB-T, the principal standard for terrestrial broadcast of digital video in Europe, has been extremely successful in leading to governments reconsidering their targets for analogue television broadcast switch-off. To enable one further small step in creating increasingly cost effective chipsets, the ODFM deterministic equalizer has been presented before with its application to DVB-T. This paper discusses the test set-up of a DVB-T compliant baseband simulation that includes the deterministic equalizer and DVB-T standard propagation channels. This is then followed by a presentation of the found inner and outer Bit Error Rate (BER) results using various modulation levels, coding rates and propagation channels in order to ascertain the actual performance of the deterministic equalizer(1).

Link between DOC in near surface peat and stream water in an upland catchment

Hydrologic transport of dissolved organic carbon (DOC) from peat soils may differ to organo-mineral soils in how they responded to changes in flow, because of differences in soil profile and hydrology. In well-drained organo-mineral soils, low flow is through the lower mineral layer where DOC is absorbed and high flow is through the upper organic layer where DOC is produced. DOC concentrations in streams draining organo-mineral soils typically increase with flow. In saturated peat soils, both high and low flows are through an organic layer where DOC is produced. Therefore, DOC in stream water draining peat may not increase in response to changes in flow as there is no switch in flow path between a mineral and organic layer. To verify this, we conducted a high-resolution monitoring study of soil and stream water at an upland peat catchment in northern England. Our data showed a strong positive correlation between DOC concentrations at − 1 and − 5 cm depth and stream water, and weaker correlations between concentrations at − 20 to − 50 cm depth and stream water. Although near surface organic material appears to be the key source of stream water DOC in both peat and organo-mineral soils, we observed a negative correlation between stream flow and DOC concentrations instead of a positive correlation as DOC released from organic layers during low and high flow was diluted by rainfall. The differences in DOC transport processes between peat and organo-mineral soils have different implications for our understanding of long-term changes in DOC exports. While increased rainfall may cause an increase in DOC flux from peat due to an increase in water volume, it may cause a decrease in concentrations. This response is contrary to expected changes in DOC exports from organo-mineral soils, where increase rainfall is likely to result in an increase in flux and concentration.

Altered expression of cell cycle proteins and prolonged duration of cardiac myocyte hyperplasia in p27KIP1 knockout mice

The precise role of cell cycle-dependent molecules in controlling the switch from cardiac myocyte hyperplasia to hypertrophy remains to be determined. We report that loss of p27(KIP1) in the mouse results in a significant increase in heart size and in the total number of cardiac myocytes. In comparison to p27(KIP1)+/+ myocytes, the percentage of neonatal p27(KIP1)-/- myocytes in S phase was increased significantly, concomitant with a significant decrease in the percentage of G(0)/G(1) cells. The expressions of proliferating cell nuclear antigen, G(1)/S and G(2)/M phase-acting cyclins, and cyclin-dependent kinases (CDKs) were upregulated significantly in ventricular tissue obtained from early neonatal p27(KIP1)-/- mice, concomitant with a substantial decrease in the expressions of G(1) phase-acting cyclins and CDKs. Furthermore, mRNA expressions of the embryonic genes atrial natriuretic factor and alpha-skeletal actin were detectable at significant levels in neonatal and adult p27(KIP1)-/- mouse hearts but were undetectable in p27(KIP1)+/+ hearts. In addition, loss of p27(KIP1) was not compensated for by the upregulation of other CDK inhibitors. Thus, the loss of p27(KIP1) results in prolonged proliferation of the mouse cardiac myocyte and perturbation of myocyte hypertrophy.

Expressions and activities of cell cycle regulatory molecules during the transition from myocyte hyperplasia to hypertrophy

The role of cell cycle dependent molecules in controlling the switch from cardiac myocyte hyperplasia to hypertrophy remains unclear, although in the rat this process occurs between day 3 and 4 after birth. In this study we have determined (1) cell cycle profiles by fluorescence activated cell sorting (FACS); and (2) expressions, co-expressions and activities of a number of cyclins, cyclin-dependent kinases (CDKs) and CDK inhibitors by reverse transcriptase-polymerase chain reaction (RT-PCR), immunoblotting andin vitrokinase assays in freshly isolated rat cardiac myocytes obtained from 2, 3, 4 and 5-day-old animals. The percentage of myocytes found in the S phase of the cell cycle decreased significantly during the transition from hyperplasia to hypertrophy (5.5, 3.5, 2.3 and 1.9% of cells in 2-, 3-, 4- and 5-day-old myocytes, respectively,P<0.05), concomitant with a significant increase in the percentage of G0/G1phase cells. At the molecular level, the expressions and activities of G1/S and G2/M phase acting cyclins and CDKs were downregulated significantly during the transition from hyperplasia to hypertrophy, whereas the expressions and activities of G1phase acting cyclins and CDKs were upregulated significantly during this transition. In addition, p21CIP1- and p27KIP1- associated CDK kinase activities remained relatively constant when histone H1 was used as a substrate, whereas phosphorylation of the retinoblastoma protein was upregulated significantly during the transition from hyperplasia to hypertrophy. Thus, there is a progressive and significant G0/G1phase blockade during the transition from myocyte hyperplasia to hypertrophy. Whilst CDK2 and cdc2 may be pivotal in the withdrawal of cardiac myocytes from the cell cycle, CDK4 and CDK6 may be critical for maintaining hypertrophic growth of the myocyte during development.

A hypoplastic model of skeletal muscle development displaying reduced foetal myoblast cell numbers, increased oxidative myofibres and improved specific tension capacity

The major component of skeletal muscle is the myofibre. Genetic intervention inducing over-enlargement of myofibres beyond a certain threshold through acellular growth causes a reduction in the specific tension generating capacity of the muscle. However the physiological parameters of a genetic model that harbours reduced skeletal muscle mass have yet to be analysed. Genetic deletion of Meox2 in mice leads to reduced limb muscle size and causes some patterning defects. The loss of Meox2 is not embryonically lethal and a small percentage of animals survive to adulthood making it an excellent model with which to investigate how skeletal muscle responds to reductions in mass. In this study we have performed a detailed analysis of both late foetal and adult muscle development in the absence of Meox2. In the adult, we show that the loss of Meox2 results in smaller limb muscles that harbour reduced numbers of myofibres. However, these fibres are enlarged. These myofibres display a molecular and metabolic fibre type switch towards a more oxidative phenotype that is induced through abnormalities in foetal fibre formation. In spite of these changes, the muscle from Meox2 mutant mice is able to generate increased levels of specific tension compared to that of the wild type.

Switching on a two-dimensional time-harmonic scalar wave in the presence of a diffracting edge

This paper concerns the switching on of two-dimensional time-harmonic scalar waves. We first review the switch-on problem for a point source in free space, then proceed to analyse the analogous problem for the diffraction of a plane wave by a half-line (the ‘Sommerfeld problem’), determining in both cases the conditions under which the field is well-approximated by the solution of the corresponding frequency domain problem. In both cases the rate of convergence to the frequency domain solution is found to be dependent on the strength of the singularity on the leading wavefront. In the case of plane wave diffraction at grazing incidence the frequency domain solution is immediately attained along the shadow boundary after the arrival of the leading wavefront. The case of non-grazing incidence is also considered.

Explaining the 'health check' of the Common Agricultural Policy: budgetary politics, globalisation and paradigm change revisited

Three potential explanations of past reforms of the Common Agricultural Policy (CAP) can be identified in the literature: a budget constraint, pressure from General Agreement on Tariffs and Trade/World Trade Organization (GATT/WTO) negotiations or commitments and a paradigm shift emphasising agriculture’s provision of public goods. This discussion on the driving forces of CAP reform links to broader theoretical questions on the role of budgetary politics, globalisation of public policy and paradigm shift in explaining policy change. In this article, the Health Check reforms of 2007/2008 are assessed. They were probably more ambitious than first supposed, although it was a watered-down package agreed by ministers in November 2008. We conclude that the Health Check was not primarily driven by budget concerns or by the supposed switch from the state-assisted to the multifunctional policy paradigm. The European Commission’s wish to adopt an offensive negotiating stance in the closing phases of the Doha Round was a more likely explanatory factor. The shape and purpose of the CAP post-2013 is contested with divergent views among the Member States.

Coupling thin layer electrochemistry with epifluorescence microscopy: an expedient way of investigating electrofluorochromism of organic dyes

The first example of thin layer electrochemistry coupled to epifluorescence microscopy in the total internal reflectance mode is described and applied to the investigation of electrochemically modulated fluorescence of an organic dye (chloromethoxytetrazine) in solution. This technique allows to generate full redox switch of fluorescence when converting reversibly the dye into its anion radical, as well as to record the spectral features of the electrogenerated species. Recording simultaneously fluorescence intensity and lifetime along with coulombic charge as a function of the electrode potential will lead to a deep insight into the redox quenching mechanism.

Life histories of academics who become heads of department: socialisation, identity and career trajectory

Although the role of the academic head of department (HoD) has always been important to university management and performance, an increasing significance given to bureaucracy, academic performance and productivity, and government accountability has greatly elevated the importance of this position. Previous research and anecdotal evidence suggests that as academics move into HoD roles, usually with little or no training, they experience a problem of struggling to adequately manage key aspects of their role. It is this problem – and its manifestations – that forms the research focus of this study. Based on the research question, “What are the career trajectories of academics who become HoDs in a selected post-1992 university?” the study aimed to achieve greater understanding of why academics become HoDs, what it is like being a HoD, and how the experience influences their future career plans. The study adopts an interpretive approach, in line with social constructivism. Edited topical life history interviews were undertaken with 17 male and female HoDs, from a range of disciplines, in a post-1992 UK university. These data were analysed using coding, categorisation and theme formation techniques and developing profiles of each of the respondents. The findings from this study suggest that academics who become HoDs not only need the capacity to assume a range of personal and professional identities, but need to regularly adopt and switch between them. Whether individuals can successfully balance and manage these multiple identities, or whether they experience major conflicts and difficulties within or between them, greatly affects their experiences of being a HoD and may influence their subsequent career decisions. It is claimed that the focus, approach and analytical framework - based on the interrelationships between the concepts of socialisation, identity and career trajectory - provide a distinct and original contribution to knowledge in this area. Although the results of this study cannot be generalised, the findings may help other individuals and institutions move towards a firmer understanding of the academic who becomes HoD - in relation to theory, practice and future research.