Electrospray ionization mass spectrometric fragmentation of hydroquinone derivatives

The fragmentation patterns of nine di-, tri- and tetracyclic hydroquinones with potential antitumor activity were rationalized by invoking competing mechanisms that included sterically accelerated homolytic cleavage, Meerwein-type rearrangements and dehydrations through elimination or intramolecular nucleophilic substitution.     

Degradation of Cephaloridine on Alkaline Hydrolysis

A kinetic study on the alkaline hydrolysis of cephaloridine ( 1 ) at pH 10.5 and 37° was carried out using ion-pair reversed-phase HPLC. The main resulting degradation products, the 7-epimer 2 of 1 , the Δ²-isomer 3 of 1 , and the 3-methylidene compound 4 were identified. The presence of a pyridinio group at C(3¹) results in a slightly increased formation constant for the 3-methylidene compound 4 and the 7-epimer 2, and introduces a new reaction: the isomerization of the double bond at C(3) in the dihydrothiazine ring to C(2).     

The oscillopolarographic determination of uranium and thorium in supporting electrolytes containing cupferron

Uranium(VI and IV) and thorium(IV) give cathodic indentations in supporting electrolytes prepared from 0.1M perchloric acid, 0.5 M ammonium thiocyanate and 5·10^-3M cupferron (solution A) or from 0.1 M succinic-succinate buffer pH 4, 0.1 M sodium chloride, 10^-3M cupferron and 0.05% gelatine (solution B). The uranium indentation on the dE/dt = f(E) curve (Q=0.75 and 0.73) permits its detection at the 3·10^-7M level. The thorium indentation (Q=0.78) permits its detection at the 4·10^-7M level in solution B. Methods for the elimination of interfering ions for the uranium determination are described. In the determination of thorium, Ga(III), Fe(III), Ti(IV) and U(VI) interfere.     

A higher resolution edge‐based finite volume method for the simulation of the oil–water displacement in heterogeneous and anisotropic porous media using a modified IMPES method

In this article, we present a higher‐order finite volume method with a ‘Modified Implicit Pressure Explicit Saturation’ (MIMPES) formulation to model the 2D incompressible and immiscible two‐phase flow of oil and water in heterogeneous and anisotropic porous media. We used a median‐dual vertex‐centered finite volume method with an edge‐based data structure to discretize both, the elliptic pressure and the hyperbolic saturation equations. In the classical IMPES approach, first, the pressure equation is solved implicitly from an initial saturation distribution; then, the velocity field is computed explicitly from the pressure field, and finally, the saturation equation is solved explicitly. This saturation field is then used to re‐compute the pressure field, and the process follows until the end of the simulation is reached. Because of the explicit solution of the saturation equation, severe time restrictions are imposed on the simulation. In order to circumvent this problem, an edge‐based implementation of the MIMPES method of Hurtado and co‐workers was developed. In the MIMPES approach, the pressure equation is solved, and the velocity field is computed less frequently than the saturation field, using the fact that, usually, the velocity field varies slowly throughout the simulation. The solution of the pressure equation is performed using a modification of Crumpton's two‐step approach, which was designed to handle material discontinuity properly. The saturation equation is solved explicitly using an edge‐based implementation of a modified second‐order monotonic upstream scheme for conservation laws type method. Some examples are presented in order to validate the proposed formulation. Our results match quite well with others found in literature. Copyright © 2016 John Wiley & Sons, Ltd.     

Alkaline hydrolysis of cephaloridine: An 1H?NMR study. Temperature dependence of the rate constants

A kinetic study on the basic hydrolysis of cephaloridine at pD= 10.5 was carried out by using the ¹H? NMR technique. Epimerization at H₇, a nucleophilic attack of hydroxyl ion on the β-lactam carbonyl group followed by the release of the pyridine molecule, and isomerization of the double bond at position 3 in the dihydrothiazine ring were the major reactions observed. Based on the results obtained, it should be emphasized that the presence of a pyridine group at 3′ results in a slightly increased formation constant for the exo methylene compound relative to other cephalosporins with different substituents at that position. The activation energy for the epimerization constant and the cleavage of the β-lactam ring at pD 10.5 was 21.2 kcal/mol. © 1993 John Wiley & Sons, Inc.     

SOLVENT EFFECTS ON THE TAUTOMERIZATION OF 5′-DEOXYPYRIDOXAL. A PHOTOPHYSICAL STUDY

Abstract— Absorption and fluorescence spectra of 5′-deoxypyridoxal (DPL) in various pure solvents and mixtures were recorded both at room temperature and over the range10–65°C. The areas under the absorption bands were analyzed to obtain the mole fraction (f_N, f_z) of two tautomers (the zwitterionic, Z, and neutral, N, forms) in the ground state. The following spectral parameters were determined from the fluorescence spectra: Stokes shift (Δv), fluorescence quantum yield of the neutral form (Q_N), fluorescence ratio of the neutral to the zwitterionic form (ø_N/ø_Z) and the rate constant of tautomerization (k₁) from Z to N in the excited state. Some of these parameters (f_N, Δv, Q_N, k₁) were found to depend on the proton donor character of the solvent, whereas others (ø_N/ø_Z) depended on its dipole moment. Thus, the absorption and fluorescence spectra of DPL allow one to obtain information on the polarity and the concentration of –OH groups on its environment.     

Electronic structure and molecular properties of the [Mo6X8L6]; X = Cl, Br, I; L = F, Cl, Br, I clusters

Relativistic TDDFT calculations including spin orbit interactions via the ZORA approximation and solvent effects were carried out on the [Mo₆X₈L₆]²⁻ X = Cl, Br, I ; L = F, Cl, Br, I clusters. These calculations indicate that the closely spaced lowest excited states are largely centered on the cubic [Mo₆X₈]⁴⁺ core. Thus, our calculations and the electronic similarities with the strongly luminescent [Mo₆Cl₈Cl₆]²⁻, [Mo₆Br₈Br₆]²⁻ and [Mo₆I₈I₆]²⁻ clusters, suggest that the clusters [Mo₆Cl₈F₆]²⁻, [Mo₆Br₈F₆]²⁻, [Mo₆I₈F₆]²⁻, [Mo₆I₈Cl₆]²⁻ and [Mo₆I₈Br₆]²⁻ studied here might be also luminescent. The calculated bond energies and reactivity indexes indicate that the most labile clusters are those with axial iodide ligands.     

Dsc Evaluations in F.c.c. Solid Solutions of Short-range-order Kinetics As Influenced by Bound Vacancies

A modified first order kinetic law, which describes the roles of bound and unbound vacancies, is proposed in order to predict defect decay and short-range-order kinetics of quenched binary alloys during linear heating experiments. The model has been applied to differential scanning calorimetry (DSC) curves of Cu–5 at%Zn quenched from different temperatures. Activation energy for migration of solute-vacancy complexes was also assessed from the kinetics of short-range-order using DSC traces. A value of 89.5±0.32 kJ mol^–1 was obtained. The relative contribution of bound and unbound vacancies to the ordering process as influenced by quenching temperature was determined. In conjunction, a parametric study of the initial total defect concentration and effective energy for defect migration was performed in order to envisage their influence on the calculated DSC profiles. This revised version was published online in August 2006 with corrections to the Cover Date.     

Evaluation of automated synthesis for chain and step‐growth polymerizations: Can robots replace the chemists?

This article explores current challenges in the use of automated parallel synthesizers in polymeric materials research. Four types of polymerizations were investigated: carbodiimide‐mediated polyesterification, diphenol phosgenation, free radical, and reversible addition‐fragmentation chain‐transfer (RAFT). Synthetic challenges of condensation polymerization, such as liquid and solid dispensing accuracy, dropwise addition, and toxic chemical handling, were successfully met using the automated synthesizer. Both solid and liquid dosing of the diphenol and diacid were successful for polyarylate synthesis. The high precision of liquid dispensing made it possible to achieve stoichiometric balance using reagent stock solutions. For all reactions, molecular weights and their reproducibility were comparable to those obtained with manual synthesis. For RAFT polymerizations, solvent and mol ratio of chain transfer reagent to initiator were successfully optimized on the automated synthesizer and a library of over 60 polymethacrylate copolymer compositions was generated. Considerable savings in time relative to manual methods were achieved when generating polymer libraries (e.g., 4.5× faster for 96 polymethacrylates and 20× faster for 45 for polycarbonates). © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 49–58, 2009