4D variational data assimilation for locally nested models: Complementary theoretical aspects and application to a 2D shallow water model

We consider the application of a four‐dimensional variational data assimilation method to a numerical model, which employs local mesh refinement to improve its solution. We focus on structured meshes where a high‐resolution grid is embedded in a coarser resolution one, which covers the entire domain. The formulation of the nested variational data assimilation algorithm was derived in a preliminary work (Int. J. Numer. Meth. Fluids 2008; under review). We are interested here in complementary theoretical aspects. We present first a model for the multi‐grid background error covariance matrix. Then, we propose a variant of our algorithms based on the addition of control variables in the inter‐grid transfers in order to allow for a reduction of the errors linked to the interactions between the grids. These formulations are illustrated and discussed in the test case experiment of a 2D shallow water model. Copyright © 2010 John Wiley & Sons, Ltd.     

Zn[(L)Proline]2: an eligible candidate for the synthesis of xanthenediones in water

An efficient route for the condensation of aldehydes with dimedone in the presence of Zn[(L)Proline]₂ in water has been reported. Hydrophilicity of the catalyst is the main attribute of this reaction. The water‐mediated reaction using catalytic amounts of recyclable catalyst avoids the use of expensive, corrosive reagents and toxic solvents and provides operational simplicity. Moreover, column chromatography and recrystallization of product are not required as the crude products itself are very pure and hence can be used for target‐oriented synthesis on a large scale. Copyright © 2012 John Wiley & Sons, Ltd.     

A reusable CuSO4 · 5H2O/cationic 2,2′‐bipyridyl system catalyzed homocoupling of terminal alkynes in water

A reusable CuSO₄ · 5H₂O/cationic 2,2′‐bipyridyl system catalyzed the homocoupling reaction of terminal alkynes in water using I₂ as the additive in the presence or absence of tetrabutylammonium bromide, giving the 1,3‐diynes in good to high yields. After reaction, the residual aqueous solution could be reused several times. Copyright © 2011 John Wiley & Sons, Ltd.     

An accurate and efficient semi‐implicit method for section‐averaged free‐surface flow modelling

An accurate, efficient and robust numerical method for the solution of the section‐averaged De St. Venant equations of open channel flow is presented and discussed. The method consists in a semi‐implicit, finite‐volume discretization of the continuity equation capable to deal with arbitrary cross‐section geometry and in a semi‐implicit, finite‐difference discretization of the momentum equation. By using a proper semi‐Lagrangian discretization of the momentum equation, a highly efficient scheme that is particularly suitable for subcritical regimes is derived. Accurate solutions are obtained in all regimes, except in presence of strong unsteady shocks as in dam‐break cases. By using a suitable upwind, Eulerian discretization of the same equation, instead, a scheme capable of describing accurately also unsteady shocks can be obtained, although this scheme requires to comply with a more restrictive stability condition. The formulation of the two approaches allows a unified implementation and an easy switch between the two. The code is verified in a wide range of idealized test cases, highlighting its accuracy and efficiency characteristics, especially for long time range simulations of subcritical river flow. Finally, a model validation on field data is presented, concerning simulations of a flooding event of the Adige river. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis of polycyclic fused 2-quinolones in aqueous micellar system

A high yielding green protocol has been developed for the synthesis of tri-, tetra-, and pentacyclic fused 2-quinolones in micellar medium. The method is more effective compared to phase-transfer catalytic (PTC) method in terms of the yield of the product as well as the reaction time. It is operationally simple as well as environmentally benign.     

Multi‐commutated Flow‐through Multi‐optosensing: A Tool for Environmental Analysis

Abstract

Multi‐commutation, which refers to the use of solenoid valves to construct the flow network, has been widely used for providing automation in flow injection analysis. In this paper, the coupling of multi‐commutation and multi‐optosensing is developed for the analysis of two pesticides in environmental water samples, fuberidazole and o‐phenylphenol. In optosensing, the use of the solid support allows the discrimination between the analytes and other compounds that, if measuring in solution, would interfere in the analysis; in addition, the sensitivity needed when facing environmental samples is obtained. The two analytes are separated by using C₁₈ silica gel as solid support, taking into account their different kinetics of sorption/desorption when interacting with the solid support microbeads; the separation is performed in the same flow‐cell where the sensing detection is carried out (by using an additional amount of solid support in the cell itself above the irradiated microzone), so both separation and determination are integrated in the cell. The native fluorescence of fuberidazole and o‐phenylphenol was simultaneously measured at 314/356 and 250/345 nm, respectively. The detection limits obtained were 0.18 and 6.1 ng mL^?1 for fuberidazole and o‐phenylphenol respectively, with a sampling frequency of about 12 samples per hour. A recovery study was performed in waters obtained for wells and rivers, with satisfactory results.     

Optimal estimation of reactivity ratios for acrylamide/acrylic acid copolymerization

Reactivity ratios for the important acrylamide (AAm)/acrylic acid (AAc) copolymerization system exhibit considerable scatter in previously published literature, and therefore, there is a need for more definitive values for these reactivity ratios. An appropriate methodology, based on the error‐in‐variables‐model (EVM) framework along with a direct numerical integration procedure, is applied in order to determine reliable reactivity ratios. The reliability of the results is confirmed with extensive and independent replication. Furthermore, via an EVM‐based criterion for the design of experiments using mechanistic models, optimal feed compositions are calculated, and from these optimal reactivity ratios are estimated for the first time (r_AAm = 1.33 and r_AAc = 0.23) based on information from the full conversion range. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4819–4827     

Acetalization of poly(vinyl alcohol) by a fatty aldehyde in water medium: Model study,kinetics, and structure analysis

Acid catalyzed poly(vinyl alcohol) (PVA) acetalization was investigated in aqueous medium at 80 °C for a PVA concentration of 8 wt %. The reactant, 10‐undecenal, was composed of a long alkyl chain with a vinyl end group, and the functionalization reaction was studied in heterogeneous media for low reactant concentrations (from 0.33 to 2.0 mol % compared with PVA hydroxyl groups concentration). First, the reaction was scrutinized with pentane‐2,4‐diol, as a model compound of PVA. Besides the expected reaction, the oxidation of the aldehyde into 10‐undecenoic acid in the presence of water was evidenced. This carboxylic acid appeared unreactive toward esterification of pentane‐2,4‐diol and PVA in water. Characterization of acetal stereochemical structure formed on the PVA backbone was performed by NMR spectroscopy in accordance to the model approach. A protocol based on ¹H NMR analysis was developed to quantify grafted aldehyde, residual aldehyde, and created carboxylic acid through direct sampling of the reaction medium. Conversions and reaction rate constants were calculated for pH ranging from 1 to 3. Finally, the acetalization yield was found to be enhanced at low pH and, in such conditions, the oxidation reaction contribution was limited. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 661–671     

Meshing Requirements for Tidal Modeling in the Western North Atlantic

This paper presents an a posteriori approach to unstructured mesh generation via a localized truncation error analysis and applies it to the Western North Atlantic Tidal (WNAT) model domain. The WNAT model domain encompasses the Gulf of Mexico, the Caribbean Sea, and the North Atlantic Ocean east to the 60°W Meridian. Herein, we pay particular attention to the area surrounding the Bahamas.

A bathymetric data set with fine resolution is employed in seven separate linear, harmonic simulations of shallow water tidal flow for seven different tidal-forcing constituents. Each set of simulation results is used to perform a truncation error analysis of a linear, harmonic form of the depth-averaged momentum equations for each of the seven different tidal-forcing frequencies. Truncation error is then driven to a more uniform, domain-wide value by solving for local node spacing requirements. The process is built upon successful research aiming to produce unstructured grids for large-scale domains that can be used in the accurate and efficient modeling of shallow water flow. The methodology described herein can also be transferred to other modeling applications.