86 resultados para chiral auxiliary


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The costs of procurement are transaction costs which are separate from the direct costs of a project. In this paper discussion is concentrated on costs of tendering. Types of cost, including money costs and opportunity costs, short-term and long-term costs, private and social costs are defined and examined in relation to various types of product and methods of procurement. The costs of the contractor and of the client are considered and tentative conclusions drawn as to who bears these costs in the short-run and in the long run. They may fall on the parties to the process for the particular project, on other contractors and clients or on society as a whole.

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Cash retention is a common means of protecting an employer from a contractor's insolvency as well as ensuring that contractors finish the work that they start. Similarly, contractors withhold part of payments due to their sub-contractors. Larger contracts tend to be subjected to smaller rates of retention. By calculating the cost of retention as an amount per year of a contract, it is shown that retention is far more expensive for firms whose work consists of short contracts. The extra cost is multiplied when the final payment is delayed, as it often is for those whose work takes place at the beginning of a project. This may explain why it is that main contractors are a lot less interested than sub-contractors in alternatives to cash retention, such as retention bonds

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This book is aimed primarily at students for whom the study of building or civil engineering contracts forms part of a construction-based course. We have had in mind the syllabus requirements for first degrees in Building, Civil Engineering, Architecture, Quantity Surveying and Building Surveying, as well as those of postgraduate courses in Construction Management and Project Management. We have also assumed that such students will already have been introduced to the general principles of English law, especially those relating to contract and tort. As a result, while aspects of those subjects that are of particular relevance to construction are dealt with here, the reader must look elsewhere for the general legal background. In producing this third edition, we have again been greatly assisted by the many helpful comments made by reviewers and users of its predecessor. Nonetheless, our basic aim is identical to that which underpinned the first edition: to provide an explanation of the fundamental principles of construction contract law, rather than a clause-by-clause analysis of any particular standard-form contract. As a result, while we draw most frequently upon JCT 98 for our illustrations of particular points, this merely reflects the pre-eminent position occupied by that particular form of contract in the UK construction industry. We conclude by repeating our previous warning as to the dangers inherent in a little learning. Neither this book, nor the courses for which it is intended, seek to produce construction lawyers. The objective is rather to enable those who are not lawyers to resolve simple construction disputes before they become litigious, and to recognize when matters require professional legal advice. It should be the aim of every construction student to understand the legal framework sufficiently that they can instruct and brief specialist lawyers, and this book is designed to help them towards that understanding.

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The cost of tendering in the construction industry is widely suspected to be excessive, but there is little robust empirical evidence to demonstrate this. It also seems that innovative working practices may reduce the costs of undertaking construction projects and the consequent improvement in relationships should increase overall value for money. The aim of this proposed research project is to develop mechanisms for measuring the true costs of tendering based upon extensive in-house data collection undertaken in a range of different construction firms. The output from this research will enable all participants in the construction process to make better decisions about how to select members of the team and identify the price and scope of their obligations.

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Standard form contracts are typically developed through a negotiated consensus, unless they are proffered by one specific interest group. Previously published plans of work and other descriptions of the processes in construction projects tend to focus on operational issues, or they tend to be prepared from the point of view of one or other of the dominant interest groups. Legal practice in the UK permits those who draft contracts to define their terms as they choose. There are no definitive rulings from the courts that give an indication as to the detailed responsibilities of project participants. The science of terminology offers useful guidance for discovering and describing terms and their meanings in their practical context, but has never been used for defining terms for responsibilities of participants in the construction project management process. Organizational analysis enables the management task to be deconstructed into its elemental parts in order that effective organizational structures can be developed. Organizational mapping offers a useful technique for reducing text-based descriptions of project management roles and responsibilities to a comparable basis. Research was carried out by means of a desk study, detailed analysis of nine plans of work and focus groups representing all aspects of the construction industry. No published plan of work offers definitive guidance. There is an enormous amount of variety in the way that terms are used for identifying responsibilities of project participants. A catalogue of concepts and terms (a “Terminology”) has been compiled and indexed to enable those who draft contracts to choose the most appropriate titles for project participants. The purpose of this terminology is to enable the selection and justification of appropriate terms in order to help define roles. The terminology brings an unprecedented clarity to the description of roles and responsibilities in construction projects and, as such, will be helpful for anyone seeking to assemble a team and specify roles for project participants.

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In developing techniques for monitoring the costs associated with different procurement routes, the central task is disentangling the various project costs incurred by organizations taking part in construction projects. While all firms are familiar with the need to analyse their own costs, it is unusual to apply the same kind of analysis to projects. The purpose of this research is to examine the claims that new ways of working such as strategic alliancing and partnering bring positive business benefits. This requires that costs associated with marketing, estimating, pricing, negotiation of terms, monitoring of performance and enforcement of contract are collected for a cross-section of projects under differing arrangements, and from those in the supply chain from clients to consultants, contractors, sub-contractors and suppliers. Collaboration with industrial partners forms the basis for developing a research instrument, based on time sheets, which will be relevant for all those taking part in the work. The signs are that costs associated with tendering are highly variable, 1-15%, depending upon what precisely is taken into account. The research to date reveals that there are mechanisms for measuring the costs of transactions and these will generate useful data for subsequent analysis.

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Asymmetric catalysis is of paramount importance in organic synthesis and, in current practice, is achieved by means of homogeneous catalysts. The ability to catalyze such reactions heterogeneously would have a major impact both in the research laboratory and in the production of fine chemicals and pharmaceuticals, yet heterogeneous asymmetric hydrogenation of C═C bonds remains hardly explored. Very recently, we demonstrated how chiral ligands that anchor robustly to the surface of Pd nanoparticles promote asymmetric catalytic hydrogenation: ligand rigidity and stereochemistry emerged as key factors. Here, we address a complementary question: how does the enone reactant adsorb on the metal surface, and what implications does this have for the enantiodifferentiating interaction with the surface-tethered chiral modifiers? A reaction model is proposed, which correctly predicts the identity of the enantiomer experimentally observed in excess.

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The sweet natural compound monatin 1 has two stereogenic centres and the (2S,4S) absolute configuration has been attributed to the natural isomer. We obtained all four stereoisomers as pure compounds by a six-step synthetic sequence. The stereogenic centre at C-4 was introduced stereoselectively by a regio- and enantiospecific enzymatic hydrolysis of the racemic ethyl dicarboxylate 4 using a protease from Aspergillus oryzae. The absolute configuration of the intermediate products was assigned by X-ray diffraction of chiral derivatives. The stereogenic centre at C-2 was introduced non-specifically, and the resulting diastereomeric mixtures were separated by RP-HPLC. The absolute configurations of the final products were established by comparing retention times on a chiral HPLC column with those of known samples. The four stereoisomers were submitted to tasting trials and three of them, particularly the (2R,4R) isomer, were found to be intensely sweet. A sample of natural monatin analysed under the same conditions is shown to contain all the four stereoisomers. The relative stereoisomeric content in the plant, as well as the possible isomerisation of the chiral centres during extraction and manipulation of monatin samples, are important points that need to be clarified by extensive analysis of the natural extracts. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005).

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Maculalactones A, B and C from the marine cyanobacterium Kyrtuthrix maculans are amongst the only compounds based on the tribenzylbutyrolactone skeleton known in nature and (+) maculalactone A from the natural source possesses significant biological activity against various marine herbivores and marine settlers. We now report a concise synthesis of racemic maculalactone A in five steps from inexpensive starting materials. Maculalactones B and C were synthesized by a minor modification to this procedure, and the synthetic design also permitted an asymmetric synthesis of maculalactone A to be achieved in around 85% ee. The (+) and (-) enantiomers of maculalactone A were assigned, respectively, to the S and R configurations on the basis of the chiral selectivity expected for catecholborane reduction of an unsymmetrical ketone in the presence of Corey's oxazoborolidine catalyst. Surprisingly, it appeared that natural (+) maculalactone A was biosynthesized in K. maculans in a partially racemic form, comprising ca. 90-95% of the (S) enantiomer and 5-10% of its (R) enantiomer. Coincidentally therefore, the percentage enantiomeric excess of the product obtained from asymmetric synthesis almost exactly matched that found in nature. (C) 2004 Elsevier Ltd. All rights reserved.

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Superior enantioselectivity in the dihydroxylation of trans-stilbene catalysed by anchored triosmium carbonyl species without using a chiral modifier is observed inside sterically congested MCM-41 channels; this effect is more pronounced through the introduction of surface Al sites into the silicate.

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The structural transformations between cesium silver-copper cyanides under modest conditions, both in solution and in the solid state, are described. Three new cesium silver(I) copper(I) cyanides with three-dimensional (3-D) framework structures were prepared as single crystals from a one-pot reaction initially heated under hydrothermal conditions. The first product to appear, Cs3Ag2Cu3(CN)(8) (I), when left in contact with the supernatant produced CsAgCu(CN)(3) (II) and CsAgCu(CN)(3)center dot 1/3H(2)O (III) over a few months via a series of thermodynamically controlled cascade reactions. Crystals of the hydrate (III) can be dehydrated to polycrystalline CsAgCu(CN)(3) (II) on heating at 100 degrees C in a remarkable solid-state transformation involving substantial breaking and reconnection of metal-cyanide linkages. Astonishingly, the conversion between the two known polymorphs of CsAg2Cu(CN)(4), which also involves a major change in connectivity and topology, occurs at 180 degrees C as a single-crystal to single-crystal transformation. Structural features of note in these materials include the presence of helical copper-cyanide chains in (I) and (II), which in the latter compound produce a chiral material. In (II) and (III), the silver-copper cyanide networks are both self- and interpenetrating, features also seen in the known polymorphs of CsAg2Cu(CN)(4).

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Four tridentate dibasic ONO donor hydrazone ligands derived from the condensation of benzoylhydrazine with either 2-hydroxyacetophenone or its para substituted derivatives (H2L1-4, general abbreviation H2L) have been used as primary ligands and 8-hydroxyquinoline (Hhq, a bidentate monobasic ON donor species) has been used as auxiliary ligand. The reaction of [(VO)-O-IV(acac)21 with H2L in methanol followed by the addition of Hhq in equimolar ratio under aerobic condition afforded the mixed-ligand oxovanadium(V) complexes of the type [(VO)-O-V(L)(hq)] (1-4) in excellent yield. The X-ray structure of the compound [(VO)-O-V(L-4)(hq)] (4) indicates that the H2L4 ligand is bonded with vanadium meridionally in a tridentate dinegative fashion through its deprotonated phenolic-O, deprotonated enolic-O and imine-N atoms. The V-O bond length order is: oxo < phenolato < enolato. H-1 NMR spectra of 4 in CDCl3 solution indicates that it's solid-state structure is retained in solution. Complexes are diamagnetic and exhibit only ligand to metal charge transfer (LMCT) transition band near 530 nm in CH2Cl2 solution in addition to intra-ligand pi-pi* transition band near 335 rim and they display quasi-reversible one electron reduction peak near -0.10 V versus SCE in CH2Cl2 solution. lambda(max) (for LMCT transition) and the reduction peak potential (E-p(c)) values of the complexes are found to be linearly related with the Hammett (sigma) constants of the substituents in the aryloxy ring of the hydrazone ligands. lambda(max) and E-p(c) values show large dependence d lambda(max)/d sigma = 32.54 nm and dE(p)(c)/d sigma = 0.19 V, respectively, on the Hammett constant. (c) 2006 Elsevier B.V. All rights reserved.

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Hierarchical ordering in a side group liquid crystal block copolymer is investigated by differential scanning calorimetry, polarized optical microscopy, small-angle X-ray and neutron scattering (SAXS and SANS) and transmission electron microscopy (TEM). A series of block copolymers with a range of compositions was prepared by atom transfer radical polymerization, comprising a polystyrene block and a poly(methyl methacrylate) block bearing chiral cholesteryl mesogens. Smectic ordering is observed as well as microphase separation of the block copolymer. Lamellar structures were observed for far larger volume fractions than for coil-coil copolymers (up to a volume fraction of liquid crystal block, f(LC) = 0.8). A sample with f(LC) = 0.86 exhibited a hexagonal-packed cylinder morphology, as confirmed by SAXS and TEM. The matrix comprised the liquid crystal block, with the mesogens forming smectic layers. For the liquid crystal homopolymer and samples with high f(LC), a smectic-smectic phase transition was observed below the clearing point. At low temperature, the smectic phase comprises coexisting domains with monolayer S-A,S-1 coexisting with interdigitated S-A,S-d domains. At high temperature a SA,1 phase is observed. This is the only structure observed for samples with lower f(LC). These unprecedented results point to the influence of block copolymer microphase separation on the smectic ordering.

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This paper compares and contrasts, for the first time, one- and two-component gelation systems that are direct structural analogues and draws conclusions about the molecular recognition pathways that underpin fibrillar self-assembly. The new one-component systems comprise L-lysine-based dendritic headgroups covalently connected to an aliphatic diamine spacer chain via an amide bond, One-component gelators with different generations of headgroup (from first to third generation) and different length spacer chains are reported. The self-assembly of these dendrimers in toluene was elucidated using thermal measurements, circular dichroism (CD) and NMR spectroscopies, scanning electron microscopy (SEM), and small-angle X-ray scattering (SAXS). The observations are compared with previous results for the analogous two-component gelation system in which the dendritic headgroups are bound to the aliphatic spacer chain noncovalently via acid-amine interactions. The one-component system is inherently a more effective gelator, partly as a consequence of the additional covalent amide groups that provide a new hydrogen bonding molecular recognition pathway, whereas the two-component analogue relies solely on intermolecular hydrogen bond interactions between the chiral dendritic headgroups. Furthermore, because these amide groups are important in the assembly process for the one-component system, the chiral information preset in the dendritic headgroups is not always transcribed into the nanoscale assembly, whereas for the two-component system, fiber formation is always accompanied by chiral ordering because the molecular recognition pathway is completely dependent on hydrogen bond interactions between well-organized chiral dendritic headgroups.