Copolymerization of CO2 and propylene oxide under rare earth ternary catalyst: design of ligand in yttrium complex

Copolymerization of carbon dioxide and propylene oxide was carried out employing (RC6H4COO)(3)Y/glycerin/ZnEt2 (R = -H, -CH3, NO2, -OH) ternary catalyst systems. The feature of yttrium carboxylates (ligand, substituent and its position on the aromatic ring) is of great importance in the final copolymerization. Appropriate design of substituent and position of the ligand in benzoate-based yttrium complex can adjust the microstructure of aliphatic polycarbonate in a moderate degree, where the head-to-tail linkage in the copolymer is adjustable from 68.4 to 75.4%. The steric factor of the ligand in the yttrium complex is crucial for the molecular weight distribution of the copolymer, probably due to the fact that the substituent at 2 and 4-position would disturb the coordination or insertion of the monomer, lead the copolymer with broad molecular distribution. Based on the study of ultraviolet-visible spectra of the ternary catalyst in various solvents, it seems that the absorption band at 240-255 nm be closely related to the active species of the rare earth ternary catalysts.

Hybrid luminescent films obtained by covalent anchoring terbium complex to silica-based network

New monomer N-(4-carboxyphenyl)-NL-(propyltriethoxysilyl)urea (1) which acts as both a ligand for Th3+ ion and a sol-gel precursor has been synthesized and characterized by H-1 NMR, and MS. Hybrid luminescent thin films consisting of organoterbium covalently bonded to a silica-based network have been obtained in situ via a sol-gel approach. Strong line emission of Tb3+ ion was observed from the hybrid luminescent films under UV excitation.

Effective energy transfer and luminescence of LB films based on europium-substituted heteropolytungstate

The europium-substituted heteropolytungstate K13Eu(SiW11O39)(2) was successfully assembled into two lipids by LB technique for the first time. X-ray diffraction has shown a well defined lamellar for the LB films. The LB films have been characterized by fluorescence spectra and the characteristic luminescence behaviors were discussed. The ligand-metal charge transfer band could be observed in the spectra of the LB films, which could not be found in that of heteropolytungstate solid. The results of fluorescence spectra indicate the energy could be effectively transferred from ligands to the Eu3+ ions in the LB films and the luminescence efficiency was increased greatly. The influences of various lipids on the luminescence of polyoxometalates were investigated. The various interactions between monolayer and polyanions have different effect on the luminescence properties of europium-substituted heteropolytungstate.

Electroluminescence based on a beta-diketonate ternary samarium complex

The triplet energy state of the HTH [HTH: 4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl) hexane-1,3-dione] ligand was measured to be 20 400 cm(-1), which indicated that Sm(HTH)(3) phen (phen: 1,10-phenanthroline) is a good complex to produce strong PL intensity and high fluorescence yield. Electroluminescent (EL) devices using the Sm( HTH) 3 phen complex as the emissive center were fabricated by vapor deposition and spin-coating methods. The relative intensity of the EL spectra changed compared to the photoluminescence (PL) spectrum, which suggested that the luminescence mechanisms of PL and EL have differences. A luminance of 9 cd m(-2) and a higher brightness of 21 cd m(-2) were obtained from the devices ITO/TPD (40 nm)/ Sm( HTH)(3) phen (50 nm)/ PBD (30 nm)/ Al (200 nm) and ITO/PVK (40 nm)/ PVK : Sm( HTH)(3) phen (2.5 wt%, 50 nm)/ PBD (30 nm)/ Al (200 nm), respectively.

Highly efficient copper-catalyzed N-arylation of alkylamines with aryl iodides using phosphoramidite as ligand

A mild and highly efficient copper-catalyzed system for N-arylation of alkylamines with aryl iodides using binaphthol-based phosphoramidites as ligands was developed. The phosphoramidite ligands are stable, cost-effective and easily prepared from inexpensive, commercially available starting materials using a simple, efficient method. (c) 2005 Elsevier B.V. All rights reserved.

Work on the Move: mobile and nomadic working methodologies.

‘Work on the move’ is a design, process-driven methodology, which uses multiple locations within an outdoors setting and movement between locations, all of which function as learning places, confined to a specified time period. Between 2012 and 2015, a team of international Higher Education product design educators (all members of Carousel, a co-operation of Erasmus members in Zwolle, Edinburgh, Nantes, Rome, Kortrijk and Oslo), industry professionals and product design students developed and tested four case studies. Each case study was conducted in a different international location and was constructed with a different focus, to help define and refine a definitive working methodology. ‘Work on the move’ explores the influence of ‘place’ upon design, in terms of the impact it has on productivity and creative problem-solving, when working away from the traditional studio/office-based environment. It also explores the significance of shared place, when working directly with a client in situ, and experiencing the place-based influences upon their businesses. While identifying location as part of the design process, the study also seeks to understand the effects of time restriction and working in transit upon creativity and productivity, within the context of specific projects.

Application of Inductive Logic Programming to Structure-Based Drug Design

Enot, D. and King, R. D. (2003) Application of Inductive Logic Programming to Structure-Based Drug Design. 7th European Conference on Principles and Practice of Knowledge Discovery in Databases (PKDD '03). Springer LNAI 2838 p156-167

Electrochemical biosensor based on microfabricated electrode arrays for life sciences applications

In developing a biosensor, the utmost important aspects that need to be emphasized are the specificity and selectivity of the transducer. These two vital prerequisites are of paramount in ensuring a robust and reliable biosensor. Improvements in electrochemical sensors can be achieved by using microelectrodes and to modify the electrode surface (using chemical or biological recognition layers to improve the sensitivity and selectivity). The fabrication and characterisations of silicon-based and glass-based gold microelectrode arrays with various geometries (band and disc) and dimension (ranging from 10 μm-100 nm) were reported. It was found that silicon-based transducers of 10 μm gold microelectrode array exhibited the most stable and reproducible electrochemical measurements hence this dimension was selected for further study. Chemical electrodeposition on both 10 μm microband and microdisc were found viable by electro-assisted self-assembled sol-gel silica film and nanoporous-gold electrodeposition respectively. The fabrication and characterisations of on-chip electrochemical cell was also reported with a fixed diameter/width dimension and interspacing variation. With this regard, the 10 μm microelectrode array with interspacing distance of 100 μm exhibited the best electrochemical response. Surface functionalisations on single chip of planar gold macroelectrodes were also studied for the immobilisation of histidine-tagged protein and antibody. Imaging techniques such as atomic force microscopy, fluorescent microscopy or scanning electron microscope were employed to complement the electrochemical characterisations. The long-chain thiol of self-assembled monolayer with NTA-metal ligand coordination was selected for the histidine-tagged protein while silanisation technique was selected for the antibody immobilisation. The final part of the thesis described the development of a T-2 labelless immunosensor using impedimetric approach. Good antibody calibration curve was obtained for both 10 μm microband and 10 μm microdisc array. For the establishment of the T-2/HT-2 toxin calibration curve, it was found that larger microdisc array dimension was required to produce better calibration curve. The calibration curves established in buffer solution show that the microelectrode arrays were sensitive and able to detect levels of T-2/HT-2 toxin as low as 25 ppb (25 μg kg-1) with a limit of quantitation of 4.89 ppb for a 10 μm microband array and 1.53 ppb for the 40 μm microdisc array.

Electrostatic Energetics of Bacillus subtilis Ribonuclease P Protein Determined by Nuclear Magnetic Resonance-Based Histidine pKa Measurements.

The pKa values of ionizable groups in proteins report the free energy of site-specific proton binding and provide a direct means of studying pH-dependent stability. We measured histidine pKa values (H3, H22, and H105) in the unfolded (U), intermediate (I), and sulfate-bound folded (F) states of RNase P protein, using an efficient and accurate nuclear magnetic resonance-monitored titration approach that utilizes internal reference compounds and a parametric fitting method. The three histidines in the sulfate-bound folded protein have pKa values depressed by 0.21 ± 0.01, 0.49 ± 0.01, and 1.00 ± 0.01 units, respectively, relative to that of the model compound N-acetyl-l-histidine methylamide. In the unliganded and unfolded protein, the pKa values are depressed relative to that of the model compound by 0.73 ± 0.02, 0.45 ± 0.02, and 0.68 ± 0.02 units, respectively. Above pH 5.5, H22 displays a separate resonance, which we have assigned to I, whose apparent pKa value is depressed by 1.03 ± 0.25 units, which is ∼0.5 units more than in either U or F. The depressed pKa values we observe are consistent with repulsive interactions between protonated histidine side chains and the net positive charge of the protein. However, the pKa differences between F and U are small for all three histidines, and they have little ionic strength dependence in F. Taken together, these observations suggest that unfavorable electrostatics alone do not account for the fact that RNase P protein is intrinsically unfolded in the absence of ligand. Multiple factors encoded in the P protein sequence account for its IUP property, which may play an important role in its function.

A review of the methodologies used in the computer simulation of evacuation from the built environment

Computer based analysis of evacuation can be performed using one of three different approaches, namely optimisation, simulation or risk assessment. Furthermore, within each approach different means of representing the enclosure, the population, and the behaviour of the population are possible. The myriad of approaches which are available has led to the development of some 22 different evacuation models. This article attempts to describe each of the modelling approaches adopted and critically review the inherent capabilities of each approach. The review is based on available published literature.

A review of the methodologies used in evacuation modelling

Computer based analysis of evacuation can be performed using one of three different approaches, namely optimization, simulation and risk assessment. Furthermore, within each approach different means of representing the enclosure, the population and the behaviour of the population are possible. The myriad of approaches that are available has led to the development of some 22 different evacuation models. This review attempts to describe each of the modelling approaches adopted and critically review the inherent capabilities of each approach. The review is based on available published literature.

Making sense of game based user data: learning analytics in applied games

Digital learning games are useful educational tools with high motivational potential. With the application of games for instruction there comes the need of acknowledging learning game experiences also in the context of educational assessment. Learning analytics provides new opportunities for supporting assessment in and of educational games. We give an overview of current learning analytics methods in this field and reflect on existing challenges. An approach of providing reusable software assets for interaction assessment and evaluation in games is presented. This is part of a broader initiative of making available advanced methodologies and tools for supporting applied game development.

Toward autonomous measurements of photosynthetic electron transport rates: An evaluation of active fluorescence-based measurements of photochemistry

This study presents a methods evaluation and intercalibration of active fluorescence-based measurements of the quantum yield ( inline image) and absorption coefficient ( inline image) of photosystem II (PSII) photochemistry. Measurements of inline image, inline image, and irradiance (E) can be scaled to derive photosynthetic electron transport rates ( inline image), the process that fuels phytoplankton carbon fixation and growth. Bio-optical estimates of inline image and inline image were evaluated using 10 phytoplankton cultures across different pigment groups with varying bio-optical absorption characteristics on six different fast-repetition rate fluorometers that span two different manufacturers and four different models. Culture measurements of inline image and the effective absorption cross section of PSII photochemistry ( inline image, a constituent of inline image) showed a high degree of correspondence across instruments, although some instrument-specific biases are identified. A range of approaches have been used in the literature to estimate inline image and are evaluated here. With the exception of ex situ inline image estimates from paired inline image and PSII reaction center concentration ( inline image) measurements, the accuracy and precision of in situ inline image methodologies are largely determined by the variance of method-specific coefficients. The accuracy and precision of these coefficients are evaluated, compared to literature data, and discussed within a framework of autonomous inline image measurements. This study supports the application of an instrument-specific calibration coefficient ( inline image) that scales minimum fluorescence in the dark ( inline image) to inline image as both the most accurate in situ measurement of inline image, and the methodology best suited for highly resolved autonomous inline image measurements.

Recyclable copper catalysts based on imidazolium-tagged bis(oxazolines): A marked enhancement in rate and enantioselectivity for Diels-Alder reactions in ionic liquid

Imidazolium-tagged bis(oxazolines) have been prepared and used as chiral ligands in the copper(II)-catalysed Diels-Alder reaction of N-acryloyl- and N-crotonoyloxazolidinones with cyclopentadiene and 1,3-cyclohexadiene in the ionic liquid 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, [emim][NTf2]. A significant and substantial enhancement in the rate and enantioselectivity was achieved in [emim][NTf2] compared with dichloromethane. For example, complete conversion and enantioselectivities up to 95 % were obtained for the reaction between N-acryloyloxazolidinone and cyclopentadiene within 2 min in [emim][NTf2] whereas the corresponding reaction in dichloromethane required 60 min to reach completion and gave an ee of only 16 %. The enhanced rates obtained in the ionic liquid enabled a catalyst loading as low as 0.5 mol % to give complete conversion within 2 min while retaining the same level of enantioselectivity. The imidazolium-tagged catalysts can be recycled ten times without any loss in activity or enantioselectivity and showed much higher affinity for the ionic liquid phase during the recycle procedure than the analogous uncharged ligand.

A Survey of Search Methodologies and Automated System Development for Examination Timetabling

Exam timetabling is one of the most important administrative activities that takes place in academic institutions. In this paper we present a critical discussion of the research on exam timetabling in the last decade or so. This last ten years has seen an increased level of attention on this important topic. There has been a range of significant contributions to the scientific literature both in terms of theoretical andpractical aspects. The main aim of this survey is to highlight the new trends and key research achievements that have been carried out in the last decade.We also aim to outline a range of relevant important research issues and challenges that have been generated by this body of work.

We first define the problem and review previous survey papers. Algorithmic approaches are then classified and discussed. These include early techniques (e.g. graph heuristics) and state-of-the-art approaches including meta-heuristics, constraint based methods, multi-criteria techniques, hybridisations, and recent new trends concerning neighbourhood structures, which are motivated by raising the generality of the approaches. Summarising tables are presented to provide an overall view of these techniques. We discuss some issues on decomposition techniques, system tools and languages, models and complexity. We also present and discuss some important issues which have come to light concerning the public benchmark exam timetabling data. Different versions of problem datasetswith the same name have been circulating in the scientific community in the last ten years which has generated a significant amount of confusion. We clarify the situation and present a re-naming of the widely studied datasets to avoid future confusion. We also highlight which research papershave dealt with which dataset. Finally, we draw upon our discussion of the literature to present a (non-exhaustive) range of potential future research directions and open issues in exam timetabling research.