Photophysics of Re(I) and Ru(II) diimine complexes covalently linked to pyrene: Contributions from intra-ligand charge transfer states

The photophysical properties of Ru(II) and Re(I) polypyridyl complexes including a bis-bipyridyl pyrene ligand are presented. The complexes ([(bpy)(2)Ru](2)bpb)(4+) and [(CO)(3)ReCl(bpb)] (bpy = 2,2'-bipyridine, bpb = 1,6-bis-(4-(2,2'-bipyrid-yl)-pyrene) were designed with the intent of examining intramolecular energy migration between MLCT states localized on the metal complexes and pyrene-localized (3)(pi-pi) states. Absorption spectroscopy of both complexes containing the bpb ligand reveals that in addition to the MLCT and the pyrene-centered (1)(pi-pi) transitions, a new absorption band is observed near 400 nm for both complexes. Absorption spectral data for the Re(I) complex strongly suggest the presence of a pyrene(pi) to bpy(pi) intraligand charge transfer (ILCT) transition. Emission spectra at room temperature and at 77 K are almost identical for the Ru(II) and Re(I) complexes containing the bpb ligand. The (3)MLCT emission of related bipyridyl compounds lacking the pyrene is observed at higher energy than for the pyrene-containing complexes, ([(bpy)(2)Ru](2)bpb)(4+) and [(CO(3)ReCl(bpb)]. The Ru(II) complex emits at room temperature with a remarkably long lifetime (130 micros in degassed DMSO). This emission is also strongly sensitive to oxygen and is almost entirely quenched in an aerated solution. In addition, excited-state absorption spectra exhibit features not consistent with (3)MLCT or (3)(pi-pi) states of the parent chromophores. The combined characteristics suggest the emission arises from either (3)(pi-pi) or (3)ILCT states or a state with mixed parentage.

Multicenter randomized trial of dacarbazine alone or in combination with two different doses and schedules of interferon alfa-2a in the treatment of advanced melanoma

Purpose: Some phase II studies have suggested that the combination of interferons (IFNs) with dacarbazine (DTIC) in the treatment of malignant melanoma (MM) increases the antitumor activity of DTIC alone. In an attempt to confirm this hypothesis, a randomized study was performed with the further intent of observing whether low doses of recombinant interferon alfa-2a (rIFNα2a) could be as effective as intermediate doses. Patients and Methods: Two hundred sixty-six patients were randomized onto three different treatment arms: DTIC 800 mg/m 2 intravenously (IV) days 1 and 21; DTIC plus rIFNα2a 9 mIU intramuscularly (IM) daily; and DTIC plus rIFNα2a 3 mIU IM three times per week. Major prognostic factors were well balanced among the three arms. Chemotherapy was administered for a maximum of eight cycles. After 6 months of therapy, rIFNα2a was continued until disease progression at 3 mIU three times per week in responding patients who had received the combined treatment. Results: The percentage of objective responses did not differ among the three groups (20%, 28%, and 23%, respectively), although a significant prolongation of response duration was observed when rIFNα2a was added to DTIC (2.6 v 8.4 v 5.5 months, respectively). However, this improvement in response duration did not translate into an amelioration of overall survival. The addition of rIFNα2a led to the onset of flu-like syndrome, but in no case was it necessary to withdraw the treatment program and no toxic deaths or life-threatening toxicities were reported. Conclusion: In this study, rIFNα2a significantly prolonged response duration, whereas no effects on response rate and survival were observed; rIFNα2a 3 mIU appeared to be equally effective and better tolerated than 9 mIU.

Factores que afectan los rendimientos en la región maicera Argentina

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The development of parallel implementation for a CFD based fire field model utilising conventional office based PCs

Parallel processing techniques have been used in the past to provide high performance computing resources for activities such as fire-field modelling. This has traditionally been achieved using specialized hardware and software, the expense of which would be difficult to justify for many fire engineering practices. In this article we demonstrate how typical office-based PCs attached to a Local Area Network has the potential to offer the benefits of parallel processing with minimal costs associated with the purchase of additional hardware or software. It was found that good speedups could be achieved on homogeneous networks of PCs, for example a problem composed of ~100,000 cells would run 9.3 times faster on a network of 12 800MHz PCs than on a single 800MHz PC. It was also found that a network of eight 3.2GHz Pentium 4 PCs would run 7.04 times faster than a single 3.2GHz Pentium computer. A dynamic load balancing scheme was also devised to allow the effective use of the software on heterogeneous PC networks. This scheme also ensured that the impact between the parallel processing task and other computer users on the network was minimized.

Parallel CFD fire modelling on office PCs with dynamic load balancing

Parallel processing techniques have been used in the past to provide high performance computing resources for activities such as Computational Fluid Dynamics. This is normally achieved using specialized hardware and software, the expense of which would be difficult to justify for many fire engineering practices. In this paper, we demonstrate how typical office-based PCs attached to a local area network have the potential to offer the benefits of parallel processing with minimal costs associated with the purchase of additional hardware or software. A dynamic load balancing scheme was devised to allow the effective use of the software on heterogeneous PC networks. This scheme ensured that the impact between the parallel processing task and other computer users on the network was minimized thus allowing practical parallel processing within a conventional office environment. Copyright © 2006 John Wiley & Sons, Ltd.

Penalties on car rental agreements

Examines the Cambridge County Court ruling in Volkswagen Financial Services (UK) Ltd v Ramage on whether a clause in a car hire contract which allowed the finance company, upon repudiation of the contract after the hirer fell into arrears, to claim compensation equivalent to the lost future rental payments was unenforceable as a penalty clause, rather than being a reasonable pre-estimate of actual loss. Refers to case law including the Court of Appeal ruling in Anglo Auto Finance Co v James in considering the differing losses which would occur during the course of the hire term according to the natural depreciation of the value of the car. Notes the reasoning of the Court on: (1) contracts of hire compared with hire purchase agreements; (2) the comparative position of the parties and the freedom to contract elsewhere; and (3) the reasonable prediction of future losses.

Beneficial ownership and detriment

Considers the factors which contribute to a court finding that a cohabitee has a beneficial interest in property, in particular the detriment which is required to establish a constructive trust, with reference to the Chancery Division decision in Levi v Levi and previous case law. Outlines the provisions on express or inferred common intention. Considers whether a loan of money from the non-owning to the owning cohabitant, made at a lower level than commercial loans, towards the purchase the property was sufficient detriment to entitle her to proceeds of sale from the property.

Returning to deposits...

Examines the Court of Appeal ruling in Midill (97PL) Ltd v Park Lane Estates Ltd on whether the court should exercise its discretion to return a deposit paid under a contract for the sale of a property where, despite the claimant having defaulted on its purchase, the owner obtained a higher price than would have been paid by the claimant when it subsequently sold the property to a third party. Considers the need for special or exceptional circumstances to be present to override the rule that deposits were to be forfeited upon the purchaser's default.

When deterrence works - and when it doesn't: a comparison of Sweden's prostitution law and UK's Dangerous Dogs Act

Many pieces of legislation have been implemented with the anticipation - or justification - that they will have a deterrent effect. Deterrence was clearly argued in the debate preceding the Swedish prostitution law prohibiting the purchase of sexual services, but less so regarding the Dangerous Dogs Act, which was a very rapid response to a particular moral panic. As it turned out, the Swedish law has had a deterrent effect on street prostitution in that 'respectable' buyers were deterred. It will be argued that it is this very 'respectability' that makes deterrence work in this case. Regarding the Dangerous Dogs Act, the owners of Pit Bulls and other banned breeds are not considered 'respectable' and the banning might have had the reversed effect - increasing the attraction of these dogs, rather than deterring the ownership. Apart from deterrence and its consequences, the rendering invisible of key actors - buyers and owners respectively - and the use of symbolic legislation to promote moral messages will also be considered. [From the Author]

The effect of bonds on loyalty towards auditors: the mediating role of commitment

The study examines the impact of knowledge and social bonds on commitment and behavioural loyalty in auditor-client relationships. A model is proposed and tested using data collected from stock exchange company executives in the UK. The results show the significant effects of the knowledge and social bonds on commitment. Commitment is shown to be a mediating variable, which influences word-of-mouth and continuance but not the purchase of non-audit services. In the light of these findings, suggestions are provided to auditors in developing relationship bonds and managing the relationship at the firm level.

English Channel towed sledge seabed images. Phase 1: scoping study and example analysis

During the 1970’s and 1980’s, the late Dr Norman Holme undertook extensive towed sledge surveys in the English Channel and some in the Irish Sea. Only a minority of the resulting images were analysed and reported before his death in 1989 but logbooks, video and film material has been archived in the National Marine Biological Library (NMBL) in Plymouth. A scoping study was therefore commissioned by the Joint Nature Conservation Committee and as a part of the Mapping European Seabed Habitats (MESH) project to identify the value of the material archived and the procedure and cost to undertake further work. The results of the scoping study are: 1. NMBL archives hold 106 videotapes (reel-to-reel Sony HD format) and 59 video cassettes (including 15 from the Irish Sea) in VHS format together with 90 rolls of 35 mm colour transparency film (various lengths up to about 240 frames per film). These are stored in the Archive Room, either in a storage cabinet or in original film canisters. 2. Reel-to-reel material is extensive and had already been selectively copied to VHS cassettes. The cost of transferring it to an accepted ‘long-life’ medium (Betamax) would be approximately £15,000. It was not possible to view the tapes as a suitable machine was not located. The value of the tapes is uncertain but they are likely to become beyond salvation within one to two years. 3. Video cassette material is in good condition and is expected to remain so for several more years at least. Images viewed were generally of poor quality and the speed of tow often makes pictures blurred. No immediate action is required. 4. Colour transparency films are in good condition and the images are very clear. They provide the best source of information for mapping seabed biotopes. They should be scanned to digital format but inexpensive fast copying is problematic as there are no between-frame breaks between images and machines need to centre the image based on between-frame breaks. The minimum cost to scan all of the images commercially is approximately £6,000 and could be as much as £40,000 on some quotations. There is a further cost in coding and databasing each image and, all-in-all it would seem most economic to purchase a ‘continuous film’ scanner and undertake the work in-house. 5. Positional information in ships logs has been matched to films and to video tapes. Decca Chain co-ordinates recorded in the logbooks have been converted to latitude and longitude (degrees, minutes and seconds) and a further routine developed to convert to degrees and decimal degrees required for GIS mapping. However, it is unclear whether corrections to Decca positions were applied at the time the position was noted. Tow tracks have been mapped onto an electronic copy of a Hydrographic Office chart. 6. The positions of start and end of each tow were entered to a spread sheet so that they can be displayed on GIS or on a Hydrographic Office Chart backdrop. The cost of the Hydrographic Office chart backdrop at a scale of 1:75,000 for the whole area was £458 incl. VAT. 7. Viewing all of the video cassettes to note habitats and biological communities, even by an experienced marine biologist, would take at least in the order of 200 hours and is not recommended. English Channel towed sledge seabed images. Phase 1: scoping study and example analysis. 6 8. Once colour transparencies are scanned and indexed, viewing to identify seabed habitats and biological communities would probably take about 100 hours for an experienced marine biologist and is recommended. 9. It is expected that identifying biotopes along approximately 1 km lengths of each tow would be feasible although uncertainties about Decca co-ordinate corrections and exact positions of images most likely gives a ±250 m position error. More work to locate each image accurately and solve the Decca correction question would improve accuracy of image location. 10. Using codings (produced by Holme to identify different seabed types), and some viewing of video and transparency material, 10 biotopes have been identified, although more would be added as a result of full analysis. 11. Using the data available from the Holme archive, it is possible to populate various fields within the Marine Recorder database. The overall ‘survey’ will be ‘English Channel towed video sled survey’. The ‘events’ become the 104 tows. Each tow could be described as four samples, i.e. the start and end of the tow and two areas in the middle to give examples along the length of the tow. These samples would have their own latitude/longitude co-ordinates. The four samples would link to a GIS map. 12. Stills and video clips together with text information could be incorporated into a multimedia presentation, to demonstrate the range of level seabed types found along a part of the northern English Channel. More recent images taken during SCUBA diving of reef habitats in the same area as the towed sledge surveys could be added to the Holme images.

Prioritization of knowledge needs for sustainable aquaculture: a national and global perspective

Aquaculture is currently the fastest expanding global animal food production sector and is a key future contributor to food security. An increase in food security will be dependent upon the development and improvement of sustainable practices. A prioritization exercise was undertaken, focusing on the future knowledge needs to underpin UK sustainable aquaculture (both domestic and imported products) using a ‘task force’ group of 36 ‘practitioners’ and 12 ‘research scientists’ who have an active interest in sustainable aquaculture. A long list of 264 knowledge needs related to sustainable aquaculture was developed in conjunction with the task force. The long list was further refined through a three stage process of voting and scoring, including discussions of each knowledge need. The top 25 knowledge needs are presented, as scored separately by ‘practitioners’ or ‘research scientists’. There was similar agreement in priorities identified by these two groups. The priority knowledge needs will provide guidance to structure ongoing work to make science accessible to practitioners and help to prioritize future science policy needs and funding. The process of knowledge exchange, and the mechanisms by which this can be achieved, effectively emerged as the top priority for sustainable aquaculture. Viable alternatives to wild fish-based aquaculture feeds, resource constraints that will potentially limit expansion of aquaculture, sustainable offshore aquaculture and the treatment of sea lice also emerged as strong priorities. Although the exercise was focused on UK needs for sustainable aquaculture, many of the emergent issues are considered to have global application.

‘Reason’ and ‘tickle’ as pragmatic constructs in the discourse of advertising

This paper explores certain pragmatic features of advertising discourse. It focuses on and expands upon a binary distinction between types of advertising discourse which was proposed initially by Bernstein (1974) and which has been touched upon more recently by other commentators such as Cook (1992). This is the distinction between reason advertisements (those which suggest a motive or reason for purchase) and tickle advertisements (those which appeal to humour, emotion and mood). It will be argued that Bernstein's distinction can be accommodated relatively systematically within contemporary frameworks of language and discourse. Drawing on a range of work in pragmatics and in systemic-functional linguistics, this paper takes some tentative steps towards the development of a theoretical model with accounts for this particular communicative-cognitive dimension of advertising discourse.

Client's assessment of architects' performance in building delivery process: Evidence from Nigeria

The overall intent of this research is to provide architects with information that can be used to improve their performance so as to optimally satisfy the client's requirements and achieve high-quality overall project performance in Nigerian construction industry. Architect performance criteria were identified based on literature within the domain of architect responsibilities. The assessment of architects’ performance was carried out through a questionnaire survey of clients of recently completed building projects in Nigeria. Analysis of data includes comparison of criteria using importance–performance index analysis. Factor analysis was carried out on criteria where architects are falling below average, to group and explore the latent structure of the criteria in the data. The results showed that the architect needs to focus on management skills and ability, buildability, design quality, project communication, project integration and client focus. These results would encourage architects to perform better within their full responsibilities in the building delivery process and deliver high-quality projects within Nigerian construction industry.

Improved Equivalent Frame Analysis Method for Flat Plate Structures in Vicinity of Edge Columns

This paper proposes a modification to the ACI 318-02 equivalent frame method of analysis of reinforced concrete flat plate exterior panels. Two existing code methods were examined: ACI 318 and BS 8110. The derivation of the torsional stiffness of the edge strip as proposed by ACI 318 is examined and a more accurate estimate of this value is proposed, based on both theoretical analysis and experimental results. A series of 1/3-scale models of flat plate exterior panels have been tested. Unique experimental results were obtained by measuring strains in reinforcing bars at approximately 200 selected locations in the plate panel throughout the entire loading history. The measured strains were used to calculate curvature and, hence, bending moments; these were used along with moments in the columns to assess the accuracy of the equivalent frame methods. The proposed method leads to a more accurate prediction of the moments in the plate at the column front face, at the panel midspan, and in the edge column. Registered Subscribers: View the full article. This document is available as a free download to qualified members. An electronic (PDF) version is available for purchase and download. Click on the Order Now button to continue with the download.