Glycosyl thiols are widely used in stereoselective S-glycoside synthesis. Their epimerization from 1,2-trans to 1,2-cis thiols (e.g., equatorial to axial epimerization in thioglucopyranose) was attained using TiCl, while SnCl promoted their axial-to-equatorial epimerization. The method included application for stereoselective β-d-manno- and β-l-rhamnopyranosyl thiol formation. Complex formation explains the equatorial preference when using SnCl, whereas TiCl can shift the equilibrium toward the 1,2-cis thiol via 1,3-oxathiolane formation.
Conformational constrained β-hairpin peptides are useful tool to modulate protein-protein interactions. A triazole bridge in hydrogen-bonded positions between two antiparallel strands induces a conformational stabilization of the β-hairpin peptide. The entity of the stability of the β-hairpin peptide depends on the length of the bridge.
In high-density contexts, such as urban or metropolitan areas, decision makers and mobility managers have to adopt suitable strategies to reduce the use of private cars and promote public transport. Indeed, such strategies may help abate the negative impacts of transportation systems (congestion, air and noise pollution, etc.). However, appropriate measures are only effective if based on the provision of high-quality public transport services. Such aims can be achieved by organizing public transport within an integrated framework where rail/metro services are the high-performing mobility backbone and bus services have a feeder function, increasing the geographical coverage of rail services. However, since a faulty train cannot be easily removed or overtaken, a rail/metro system is highly vulnerable to system breakdowns which could entail significant reductions in system quality. Suitable intervention strategies therefore have to be developed to manage rail system emergencies. The aim of this article is to provide a method to determine optimal intervention strategies in the case of a metro system failure. Since in real contexts an exhaustive approach has to be excluded due to the huge number of alternative solutions to be evaluated, it is necessary to adopt or develop appropriate algorithms to obtain sub-optimal solutions within suitable computational times. Hence a Neighbourhood Search Algorithm to identify the optimal solution is applied and tested in the case of a real metro line in order to show the feasibility of our proposal.
A rail system represents a useful tool for reducing flows (cars and trucks) on a road system in high density contexts (such as urban and metropolitan areas) with a view to abating greenhouse gas emissions. In particular, since rail passengers maximise their own utility, variations in mobility choices can be induced only by significantly improving the level-of-service of public transport. By defining feasibility thresholds, our proposal is to analyse the economic and environmental feasibility of a new signalling system which would increase service frequencies of a rail system, thereby reducing passenger waiting times. This approach was applied to a regional rail line in southern Italy to show the usefulness of the proposed methodology
Molecular tools to stabilize the β-hairpin conformation are needed as β-hairpin peptides are useful molecules for pharmaceutical, biological and materials applications. We explored the use of a "triazole bridge", a covalent link between two β-hairpin strands obtained through Cu-catalyzed alkyne-azide cycloaddition, combined with an aromatic-aromatic interaction. Highly conformationally stable peptides were identified by NMR screening of a small collection of cyclic peptides based on the Trpzip2 scaffold. The characteristic Trp-Trp interaction of Trpzip2 was replaced by a diagonal triazole bridge of variable length. NMR and CD analyses showed that triazole and indole rings could favorably interact to stabilize a β-hairpin conformation. The conformational stabilization depends on the length of the triazole bridge and the reciprocal position between the aromatic rings. Combining aromatic interactions and the covalent inter-strand triazole bridge is a useful strategy to obtain peptides with a high β-hairpin content.
Promoting rail systems can represent a useful policy for rebalancing modal choices and reducing private car use, especially in high density contexts. Obviously, an increase in passenger numbers is only possible if generalised costs (i.e. a weighted sum of times and monetary costs) associated to public transport are abated. According to the recent literature and current professional practice, most strategies for achieving this objective are based only on infrastructural interventions which may be unfeasible or inadequate in densely populated contexts. Likewise, the adoption of policies based on replacing existing fleets or reducing fare levels entails increases in national or regional subsidies, which would be difficult to achieve in the current economic climate.\ud
Hence, our proposal is based on investigating effects on travel demand arising from the replacement or upgrading of existing signalling systems (both in terms of trackside and on-board equipment). Indeed, the recent European Union policy to create a single transnational interoperable rail network imposes the development of innovative signalling systems. In this context, since cost-benefit analysis has to be implemented to verify the economic and environmental feasibility of the proposed intervention strategy, an appropriate method should be developed to estimate passenger flows according to future configurations. In this paper, we propose a method to determine travel demand in current and future contexts by appropriately processing data from Italy's national census on mobility, population growth forecasts and turnstile counts. The proposed approach is applied to the regional ‘Naples–Sorrento’ rail line serving the metropolitan area of Naples in southern Italy in order to show its feasibility
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