Proficiency testing scheme for the harmonization and comparability of analytical measurements

According to the experience of the successful implementation of proficiency tests (PT) by using the certified reference value as the assigned value, a new scheme of evaluation is presented by suggesting the use of the uncertainty associated with the certified value. The technical performance of laboratories is evaluated by the parameter quadratic mean error (QME), which is the square root of the sum of the square of the bias and that of the standard deviation of the laboratory. This parameter is considered as the estimate of the measurement uncertainty of the laboratory and is compared to the uncertainty (U) associated with the certified value provided by an NMI. Considering that the calibration and measurement capability, known as the CMC, is recognized among NMIs, the ratio QME/U enables us to compare the PT relative to the CMC of an NMI, and, consequently, to any other comparison results based on the CMC of signatories of the mutual recognition arrangement (MRA) of the International Committee of Weights and Measure (CIPM). Presented at BERM-11, October 2007, Tsukuba, Japan.     

Coordination mechanisms for inventory control in three-echelon serial and distribution systems

This paper is concerned with the coordination of inventory control in three-echelon serial and distribution systems under decentralized control. All installations in these supply chains track echelon inventories. Under decentralized control the installations will decide upon base stock levels that minimize their own inventory costs. In general these levels do not coincide with the optimal base stock levels in the global optimum of the chain under centralized control. Hence, the total cost under decentralized control is larger than under centralized control. To remove this cost inefficiency, two simple coordination mechanisms are presented: one for serial systems and one for distribution systems. Both mechanisms are initiated by the most downstream installation(s). The upstream installation increases its base stock level while the downstream installation compensates the upstream one for the increase of costs and provides it with a part of its gain from coordination. It is shown that both coordination mechanisms result in the global optimum of the chain being the unique Nash equilibrium of the corresponding strategic game. Furthermore, all installations agree upon the use of these mechanisms because they result in lower costs per installation. The practical implementation of these mechanisms is discussed.     

A Conversation with Franco Rasetti

Along with Enrico Fermi, Franco Rasetti played a key role in the rebirth of Italian physics in the 1920s and 1930s. In this interview he talks about his experiments at Caltech on the Raman effect in 1928–1929, mountain climbing, his passion for bugs, fossils, and flowers, and doing physics in Florence, Rome, Berlin-Dahlem, and Quebec. Rasetti also reminisces about the Rome school of mathematics and other scientists he has known and worked with in Europe and in North America, including Robert and Glenn Millikan, Lise Meitner, and O. M. Corbino.     

Spectroscopic characterization of halogen- and cyano-substituted pyridinevinylenes synthesized without catalyst or solvent

An efficient Knoevenagel route using green chemistry conditions was applied for the synthesis of halogen- and cyano- substituted pyridinevinylene compounds. Absorption and fluorescence emission spectra of these conjugated compounds were recorded and compared in order to evaluate the effect of substituents on the electronic properties of pyridinevinylene compounds. The substituents studied were terminal Cl and F, two or three aromatic rings, as well as a cyano group attached to a C=C double bond. The compounds synthesized are: (E)-2-(4-fluorostyryl)pyridine, (E)-2-(4-chlorostyryl)pyridine, (E)-4-(4-chlorostyryl)pyridine, 2,3-diphenylacrylonitrile, 3-phenyl-2-(pyridin-2-yl)acrylonitrile, 3-phenyl-2-(pyridin-3-yl)acrylonitrile, 2-phenyl-3-(pyridin-2-yl)acrylonitrile, 3,3′-(1,4-phenylene)bis(2-phenylacrylonitrile), 3,3′-(1,4-phenylene)bis(2-(pyridin-2-yl)acrylonitrile), and 3,3′-(1,4-phenylene)bis(2-(pyridin-3-yl)acrylonitrile). The solvent-free method used in this work allows obtaining each compound by controlling the reaction temperature. The compounds were characterized by infrared spectroscopy and 1H-NMR spectroscopy.     

A theoretical study on three conformational structures of 2,6‐distyrylpyridine

Ab initio methods at the levels HF/cc‐pVDZ, HF/6‐31G(d,p), MP2/cc‐pVDZ, and MP2/6‐31G(d,p), as well as methods based on density functional theory (DFT) employing the hybrid functional B3LYP with the basis sets cc‐pVDZ and 6‐31G(d,p), have been applied to study the conformers of 2,6‐distyrylpyridine. Bond distances, bond angles, and dihedral angles have been calculated at the B3LYP level. The calculated values were in good agreement with those measured by X‐ray diffraction analysis of 2,6‐distyrylpyridine. The values calculated using the Hartree‐Fock method and second‐order perturbation theory (MP2) were inconsistent. The optimized lowest‐energy geometries were calculated from the reported X‐ray structural data by the B3LYP/cc‐pVDZ method. Three conformations, A, B, and C, were proposed for 2,6‐distyrylpyridine. Calculations at the three levels of theory indicated that conformation A was the most stable structure, with conformations C and B being higher in energy by 1.10 and 2.57 kcal/mol, respectively, using the same method and basis function. The same trend in the relative energies of the three possible conformations was observed at the two levels of theory and with the different basis sets employed. The reported X‐ray data were utilized to optimize total molecular energy of conformation A at the different calculation levels. The bond lengths, bond angles, and dihedral angles were then obtained from the optimized geometries by ab initio methods and by applying DFT using the two basis functions cc‐pVDZ and 6‐31G(d,p). The values were analyzed and compared. The calculated total energies, the relative energies of the molecular orbitals, the gap between them, and the dipole moment for each conformational structure proposed for 2,6‐distyrylpyridine are also reported. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

Total synthesis of graphislactone G

We present a total synthesis of the fungal natural product graphislactone G, a chlorinated resorcylic lactone. The key step is a Suzuki coupling used for the construction of the central biaryl bond. Graphislactone G was prepared in 13 steps with 22% yield starting with orcinol and phloroglucinic acid, where the longest linear sequence consists of nine steps.     

Experimental models for assaying microvascular endothelial cell pathophysiology in stroke

It is important to understand the molecular mechanisms underlying neuron death following stroke in order to develop effective neuroprotective strategies. Since studies on human stroke are extremely limited due to the difficulty in collecting post-mortem tissue at different time points after the onset of stroke, brain ischaemia research focuses on information derived from in-vitro models of neuronal death through ischaemic injury [1]. This review aims to provide an update on the different in-vitro stroke models with brain microvascular endothelial cells that are currently being used. These models provide a physiologically relevant tool to screen potential neuroprotective drugs in stroke and to study the molecular mechanisms involved in brain ischaemia.     

Anatomy of a laminar starting thermal plume at high Prandtl number

We present an experimental study of the dynamics of a plume generated from a small heat source in a high Prandtl number fluid with a strongly temperature-dependent viscosity. The velocity field was determined with particle image velocimetry, while the temperature field was measured using differential interferometry and thermochromic liquid crystals. The combination of these different techniques run simultaneously allows us to identify the different stages of plume development, and to compare the positions of key-features of the velocity field (centers of rotation, maximum vorticity locations, stagnation points) respective to the plume thermal anomaly, for Prandtl numbers greater than 10³. We further show that the thermal structure of the plume stem is well predicted by the constant viscosity model of Batchelor (Q J R Met Soc 80: 339–358, 1954) for viscosity ratios up to 50.     

Toward multipurpose NMR experiments

Standard phase cycled NMR pulse sequences were generalized such that for each individual step of the pulse phase cycle the free induction decay is stored separately without phase correction. This is in contrast to the usual practice, where pulse responses are phase shifted immediately (by applying a ‘receiver phase’) and co‐added as they are stored. The approach used here allows one to extract different types of NMR information, which are usually referred to as different ‘experiments’, from the same raw data set a posteriori by using complex linear combinations. Storing the free induction decays of individual phase cycle steps separately and using specific linear combinations of these data to obtain a particular type of information increase the overall efficiency of a given set of NMR experiments substantially, because all information can be derived from a single multiplexed data set. This ‘super‐experiment’ requires only as much time as the most complex of the derived specific experiments alone. The principle of this multipurpose approach was demonstrated by performing different multiple‐quantum filtered COSY experiments. It also becomes possible to generate linear combinations, which differ from the conventionally acquired spectra a posteriori. For example, we implemented diagonal peak reduction by using zero‐ and single‐quantum filtered COSY contributions without requiring additional experiment time. Copyright © 2009 John Wiley & Sons, Ltd.