Crystallographic report: Bis{µ‐[O‐cyclopentyl(4‐methoxyphenyl)dithiophosphonato]1κ:S,2κ:S‐[O‐cyclopentyl(4‐methoxyphenyl)dithiophosphonato]‐1κ2S,S′}dicadmium(II)

The centrosymmetric title compound, [Cd₂{CH₃OC₆H₄P(OC₅H₉)S₂}₄], features an eight‐membered [? Cd? S? P? S? ]₂ ring owing to the presence of bridging dithiolate ligands. Tetrahedral coordination geometries for cadmium are completed by chelating ligands. Copyright © 2004 John Wiley & Sons, Ltd.     

A turbidimetric method to measure isoelectric points and particles deposition onto massive substrates

A simple experimental approach was developed to determine the adhesion rate of particles onto massive substrate. Turbidimetry measurements are used to follow the evolution of particle concentration in a suspension in dynamic contact with the walls of a vessel made of different materials. This method allows to rapidly obtain qualitative results about the adhesion of metallic oxides particles on massive substrates. Adhesion of particles of charged latex onto glass was used to validate the approach and was shown to be a method to determine isoelectric points (IEP) of massive substrates. Then, the adhesion of an iron oxide (hematite) particles onto several substrates was studied to determine the reactivity of current labware (glass, polypropylene) and on a metal (aluminum) commonly found in industrial fouling problems. Adhesion of hematite was found to be pH-dependant, and occurs only below ca. 6 (glass) or 7 (polypropylene), and above 7 (aluminum). DLVO calculations were performed to model the hematite/water/glass system and are consistent with the experimental results. Experiments at temperature 7–50 °C have shown an increasing of the adhesion rate from 7 to 40 °C, then a constant value until 50 °C.     

On the Cauchy problem for some abstract nonlinear differential equations

In the present paper, we study the Cauchy problem in a Banach spaceE for an abstract nonlinear differential equation of form $$\frac{{d^2 u}}{{dt^2 }} = - A\frac{{du}}{{dt}} + B(t)u + f(t,W)$$ whereW = (A ₁(t)u,A ₂(t)u,?,A _?(t)u), (A _i (t),i = 1, 2, ?,?), (B(t),t ∈I = [0,b]) are families of closed operators defined on dense sets inE intoE, f is a given abstract nonlinear function onI ×E ^? intoE and ?A is a closed linear operator defined on dense set inE intoE, which generates a semi-group. Further, the existence and uniqueness of the solution of the considered Cauchy problem is studied for a wide class of the families (A _i(t),i = 1, 2, ?,?), (B(t),t ∈I). An application and some properties are also given for the theory of partial diferential equations.     

Kinetic and thermodynamic studies on ligand substitution reactions and base-on/base-off equilibria of cyanoimidazolylcobamide, a vitamin B12 analog with an imidazole axial nucleoside

Ligand substitution reactions of the vitamin B12 analog cyanoimidazolylcobamide, CN(Im)Cbl, with cyanide were studied. Cyanide substitutes imidazole (Im) in the alpha-position more slowly than it substitutes dimethylbenzimidazole in cyanocobalamin (vitamin B12). The kinetics of the displacement of Im by CN- showed saturation behaviour at high cyanide concentration; the limiting rate constant was found to be 0.0264 s(-1) at 25 degrees C and is characterized by the activation parameters: DeltaH(not =) = 111 +/- 2 kJ mol(-1), DeltaS(not =) = +97 +/- 6 J K(-1) mol(-1), and DeltaV(not =) = +9.3 +/- 0.3 cm3 mol(-1). These parameters are interpreted in terms of an I(d) mechanism. The equilibrium constant for the reaction of CN(Im)Cbl with CN- was found to be 861 +/- 75 M(-1), which is significantly less than that obtained for the reaction of cyanocobalamin with CN- (viz. 10(4) M(-1)). pKbase-off for the base-on/base-off equilibrium was determined spectrophotometrically and found to be 0.99 +/- 0.05, which is about 0.9 pH units higher than that obtained previously in the case of cyanocobalamin. In addition, the kinetics of the base-on/base-off reaction was studied using a pH-jump technique and the data obtained revealed evidence for an acid catalyzed reaction path. The results obtained in this study are discussed in reference to those reported previously for cyanocobalamin.     

Ligand substitution behavior of a simple model for coenzyme B12

The ligand substitution reactions of trans-[CoIII(en)2(Me)H2O]2+, a simple model for coenzyme B12, were studied for cyanide and imidazole as entering nucleophiles. It was found that these nucleophiles displace the coordinated water molecule trans to the methyl group and form the six-coordinate complex trans-[Co(en)2(Me)L]. The complex-formation constants for cyanide and imidazole were found to be (8.3 +/- 0.7) x 10(4) and 24.5 +/- 2.2 M-1 at 10 and 12 degrees C, respectively. The second-order rate constants for the substitution of water were found to be (3.3 +/- 0.1) x 10(3) and 198 +/- 13 M-1 s-1 at 25 degrees C for cyanide and imidazole, respectively. From temperature and pressure dependence studies, the activation parameters delta H++, delta S++, and delta V++ for the reaction of trans-[CoIII(en)2(Me)H2O]2+ with cyanide were found to be 50 +/- 4 kJ mol-1, 0 +/- 16 J K-1 mol-1, and +7.0 +/- 0.6 cm3 mol-1, respectively, compared to 53 +/- 2 kJ mol-1, -22 +/- 7 J K-1 mol-1, and +4.7 +/- 0.1 cm3 mol-1 for the reaction with imidazole. On the basis of reported activation volumes, these reactions follow a dissociative mechanism in which the entering nucleophile could be weakly bound in the transition state.     

Theoretical and vibrational spectroscopic analysis of the CO stretching mode of cholesteryl alkanoates: the particular case of the cholesteryl acetate

Structural and vibrational properties of the CO stretching bond of cholesteryl acetate and related steroids are investigated theoretically and by Micro-Raman spectroscopy. In this work, an analysis of the CO stretching mode for the cholesteryl acetate is presented. Experimental results in crystalline, isotropic liquid and liquid crystal phases are compared with quantum chemical calculations using semi empirical hamiltonians (AM1 and PM3) and the density functional theory. The calculations were performed on isolated molecules with different conformations as found on previous investigations giving strong evidence of their existence. Calculated frequencies are found to be very close to experiments and suggest the possible existence of the predicted conformers.     

Reactions with heterocyclic amidines. VI. Synthesis and chemistry of pyrazol-5-yl,and 1,2,4-triazol-5-ylhydrazonyl chlorides

The 4-bromo-3-phenylpyrazol-5-ylhydrazonyl chlorides (Ia,b) and 1,2,4-triazol-5-ylhydrazonyl chlorides (IIa,b) were prepared via coupling of diazotized 4-bromo-3-phenyl-5-aminopyrazole (III) and 5-amino-1,2,4-triazole (IV) with α-chloro derivatives of acetylacetone and of ethyl aceto-acetate. Compounds Ia and IIa,b were utilised for the synthesis of several new heterocyclic derivatives.     

Commutativity theorems for s-unital rings with constraints on commutators

Let R be an associative s-unital ring with the polynomial identity \( y^{s}[x^{n},y]=\pm [x,y^{m}]x^t\) or \( y^{s}[x^{n},y]=\pm x^{t}[x,y^{m}]\) , where m, n, s and t are given non-negative integers such that m > 0 or n > 0 and m ≠ n if s = m ? 1 and t = n ? 1. Using similar methods as in our recent papers [1] and [2], we prove here the commutativity of R for various values of m, n, s and t, under appropriate constraints on torsion of commutators.     

Effect of cold work on the dissolution kinetics in the precipitating Al-2 wt% Mg alloy

The fracture stress _f was taken to assess the mechanism of dissolution of the -phase in the Al-2 wt% Mg alloy. The role of pre-cold working the polycrystalline samples was investigated. The dissolution of the -phase was carried out at different temperatures. The relation between the fracture stress and the time of dissolution showed peaky curves. The rise of _f towards a maximum was attributed to the progressive dissolution of the precipitates. The position of the peak was found to shift towards lower times of dissolution with the increase of the dissolution temperature or the increase of the pre-cold work. Considering the peak position indicative of a certain degree of dissolution, equivalent times and temperatures of the dissolution mechanism were thus found and the activation energy was calculated. Pre-cold working the samples before the dissolution act decreased the activation energy responsible for the process from 1·95×10^–19 J to about 0·48× 10^–19 J. The initial drop in _f observed for heavily cold worked samples pointed towards the possible effect of excess vacancies created by cold work.The authors are really grateful for the enlightening discussions with Prof. R. Kamel.