SOLVERSTAT: a new utility for multipurpose analysis. An application to the investigation of dioxygenated Co(II) complex formation in dimethylsulfoxide solution

A new utility for multipurpose analysis, SOLVERSTAT, taking advantage of the versatility of spreadsheets is here described. By means of this tool advanced statistical tests have introduced in Microsoft Excel Solver thus allowing regression diagnostic and discrimination between different models. The utility is here applied to the determination, by UV-Vis spectroscopy, of the stability constant for the uptake of molecular dioxygen by the 1:2 complex of Co(II) with N,N′-dimethylethylenediamine (dmen) in the aprotic solvent dimethylsulfoxide (dmso) at 298 K and in a medium adjusted to 0.1 mol dm⁻³ with Et₄NClO₄. The reliability of the model and parameters obtained are discussed and the results compared with those obtained by Dynafit, a different software package, and by independent voltammetric measurements. The validity of SOLVERSTAT has been also examined applying it to the discrimination between different models already discussed in the literature.     

Approximations of inventory models

Summary A general procedure is presented for constructing approximations of discrete review single product dynamic inventory models. Bounds are derived for the approximations and compared with the ones ofHinderer [1978],Whitt [1978] for the approximation of a general dynamic program. Good order-policies are constructed. Finally, conditions are given under which the sequence of bounds associated with a sequence of approximating models converges to zero.

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Zusammenfassung Es wird ein allgemeines Verfahren zur Approximation periodisch inspizierter dynamischer Ein-Produkt-Lagerhaltungsmodelle betrachtet. Dazu werden Fehlerschranken gegeben. Diese werden verglichen mit denen vonHinderer [1978],Whitt [1978] für ein allgemeines dynamisches Entscheidungsmodell. Außerdem werden gute Bestellpolitiken konstruiert und hinreichende Bedingungen gegeben, unter denen die Fehlerschranken einer Folge von approximierenden Modellen gegen Null konvergiert.

     

Unveiling Carbon Dioxide and Ethanol Diffusion in Carbonated Water-Ethanol Mixtures by Molecular Dynamics Simulations

The diffusion of carbon dioxide (CO2) and ethanol (EtOH) is a fundamental transport process behind the formation and growth of CO2 bubbles in sparkling beverages and the release of organoleptic compounds at the liquid free surface. In the present study, CO2 and EtOH diffusion coefficients are computed from molecular dynamics (MD) simulations and compared with experimental values derived from the Stokes-Einstein (SE) relation on the basis of viscometry experiments and hydrodynamic radii deduced from former nuclear magnetic resonance (NMR) measurements. These diffusion coefficients steadily increase with temperature and decrease as the concentration of ethanol rises. The agreement between theory and experiment is suitable for CO2. Theoretical EtOH diffusion coefficients tend to overestimate slightly experimental values, although the agreement can be improved by changing the hydrodynamic radius used to evaluate experimental diffusion coefficients. This apparent disagreement should not rely on limitations of the MD simulations nor on the approximations made to evaluate theoretical diffusion coefficients. Improvement of the molecular models, as well as additional NMR measurements on sparkling beverages at several temperatures and ethanol concentrations, would help solve this issue.     

Generation and reactivity of 3‐carbethoxy‐5‐phenyl‐5H,7H‐thiazolo[3,4‐c]oxazol‐4‐ium‐1‐olate

3‐Carbethoxy‐5‐phenyl‐5H,7H‐thiazolo[3,4‐c]oxazol‐4‐ium‐1‐olate was generated from (2R,4R)‐N‐ethoxyoxalyl‐2‐phenylthiazolidine‐4‐carboxylic acid and its reactivity studied. This münchnone showed low reactivity as dipole although from the reaction with dimethyl acetylenedicarboxylate the corresponding (3R)‐3‐phenyl‐17H,3H‐pyrrolo[1,2‐c]thiazole‐5,6,7‐tricarboxylate could be isolated. The thermolysis of (2R,4R)‐N‐ethoxyoxalyl‐2‐phenylthiazolidine‐4‐carboxylic acid in refluxing acetic anhydride led to the synthesis of N‐(1‐ethoxycarbonyl‐2‐phenylvinyl)‐2‐phenyl‐4‐thioxo‐1,3‐thiazolidine. The structure of methyl (2R,4R)‐N‐ethoxyoxalyl‐2‐phenylthiazoliddine‐4‐carboxylate was determined by X‐ray crystallography.     

Controlling Antibacterial Activity Exclusively with Visible Light: Introducing a Tetra-ortho-Chloro-Azobenzene Amino Acid

The introduction of a novel tetra-ortho-chloroazobenzene amino acid (CEBA) has enabled photoswitching of the antimicrobial activity of tyrocidine A analogues by using exclusively visible light, granting spatiotemporal control under benign conditions. Compounds bearing this photoswitchable amino acid become active upon irradiation with red light, but quickly turn-off upon exposure to other visible light wavelengths. Critically, sunlight quickly triggers isomerisation of the red light-activated compounds into their original trans form, offering an ideal platform for self-deactivation upon release into the environment. Linear analogues of tyrocidine A were found to provide the best photocontrol of their antimicrobial activity, leading to compounds active against Acinetobacter baumannii upon isomerisation. Exploration of their N- and C-termini has provided insights into key elements of their structure and has allowed obtaining new antimicrobials displaying excellent strain selectivity and photocontrol.     

Selection of sampling adsorbents and optimisation and validation of a GC-MS/MS method for airborne pesticides

A methodology for the sampling and determination of airborne pesticides has been developed. The trapping efficiency of three adsorbents, namely XAD-2,XAD-4 and a sandwich sorbent (PUF-XAD2-PUF), was tested for 34 pesticides and the latter was selected because it presented the highest retention capacity without breakthrough. Pesticides were determined by gas chromatography coupled to an ion trap mass spectrometer in tandem. The method showed recoveries ranging from 70% to 120% with limits of quantification in the range of 16.1–322.6 pg m^?3 when 155 m³ were sampled. This analytical strategy was applied to 10 indoor air samples collected in dwellings from the Valencian Region. Six pesticides, namely diphenylamine, pyrimethanil, bifenthrin, lambda-cyhalothrin, permethrin and cypermethrin were detected in indoor samples with concentrations ranging from 1.46 to 22.02 ng m^?3.