Acyl and α-Ketoacyl Complexes of Pt(II) with Weak Donor Ligands

Treatment of trans-Pt(COCOPh)(Cl)(PPh₃)₂ (1a) with AgBF₄in THF led to the formation of a metastatic complex trans-[Pt(COCOPh)(THF)(PPh₃)₂](BF₄) (2) which readily underwent ligand substitution to give a cationic aqua complex trans-[Pt(COCOPh)(OH₂)(PPh₃)₂](BF₄) (5a). Complex 5a has been characterized spectroscopically and crystallographically. Analogous reaction of trans-Pt(COCOOMe)(Cl)(PPh₃)₂ (1b) with Ag(CF₃SO₃) in dried CH₂C1₂ was found first to yield a methoxyoxalyl triflato complextrans-Pt(COCOOMe)(OTf)(PPh₃)₂ (6). Attempts to crystallize the triflato product in CH₂-cl₂hexane under ambient conditions also afforded an aqua complex of the triflate salt f/wu-[Pt(COCOOMe)(OH₂)(PPhj)₂](CF₃SO₃) (5b). Complex 5a in a noncoordinating solvent such as CH₂C1₂ or CHCl₃ suffered spontaneous decarbonylation to form first cis-[Pt(COPh)(CO)(PPh₃)₂l(BF₄) (3a) then the thermodynamically stable isomer trans-[Pt(COPh)(CO)(PPh₃)₂](BF₄) (3b). Crystallization of complex 3b under ambient conditions resulted in an aqua benzoyl complex trans-[Pt(COPh)(OH₂)(PPh₃)₂](BF₄) (7). The replacement of the H_2O ligand in complex 7 by CO was done simply by bubbling CO into the solution of 7. The single crystal structures of 5b and 7 have been determined by X-ray diffraction. The distances of the Pt-O bonds in 5a, 5b, and 7 support that the aqua ligand is a weak donor in such cationic aquaorganoplatinum(lI) complexes, in agreement with their lability to the substitution reactions.     

Extended radial epiderivatives of non-convex vector-valued maps and parametric quasiconvex programming

In this paper, we consider extended vector-valued mappings defined on a normed linear space. Based on the recent semicontinuous regularizations related to hypographical and/or epigraphical profile mappings of the considered function introduced, we define semicontinuous radial epiderivatives. We, then, demonstrate that the properties of these epiderivatives amount to properties of hypographical and/or epigraphical profile mappings of the corresponding difference quotient of the underlying function, which simplify fairly well the proofs in the radial epiderivative formulaes. In particular, we stress the impact of semicontinuity, hence, we characterize with new arguments the radial epiderivatives in terms of the suprema and/or infima of the interiorly radial cone of the hypograph and/or epigraph of the considered function. Finally, we obtain optimality conditions for general non-convex constrained vector optimization problems. We apply thereafter the obtained pattern to a parametric quasiconvex programming problem for which we derive necessary and sufficient optimality conditions that are not sensitive to perturbation at the nominal level, yielding henceforth more – and strong at least under asymptotically regular constraints – information than the recent stability results obtained under additional conditions on the regularity of the normal cone to the adjusted sublevel sets of the underlying function.     

Mass Spectrometry of Some Benzylidene Imidazolidinediones and Thiazolidinediones. II- chlorobenzyl imidazolidinedione and Fluoro or Chlorobenzyl Thiazolidinedione Compounds

In the present investigation, a study of the electron impact mass spectrometry data is reported for seven compounds of a series of some 3-(4-chlorobenzyl)-5-benzylidene-imidazolidine-2, 4-diones and 3-(4-fluoro or chlorobenzyl)-5-benzylidene-thiazolidine-2, 4-diones previously synthesized.     

Numerical solutions for jump-diffusions with regime switching

This paper is devoted to numerical solutions for a class of jump-diffusions with regime switching. After briefly reviewing the notion of jump-diffusions with regime switching, finite-difference procedures are constructed. Under simple conditions, it is proved that the algorithm converges to the desired limit by means of a martingale problem formulation. Numerical experiments are carried out to demonstrate the performance of the algorithm.     

Ion Product of Pure Water Characterized by Physics-Based Water Model

Pure water has been characterized for nearly a century, by its dissociation into hydronium (H₃O)¹⁺ and hydroxide (HO)^1- ions. As a chemical equilibrium reaction, the equilibrium constant, known as the ion product or the product of the equilibrium concentration of the two ion species, has been extensively measured by chemists over the liquid water temper-ature and pressure range. The experimental data have been nonlinear least-squares fitted to chemical thermodynamic-based equilibrium equations, which have been accepted as the industrial standard for 35 years. In this study, a new and statistical-physics-based water ion product equation is presented, in which, the ions are the positively charged protons and the negatively charged proton-holes or prohols. Nonlinear least squares fits of our equation to the experimental data in the 0-100 ℃ pure liquid water range, give a factor of two better precision than the 35-year industrial standard.     

α- or β-Substituted functional phthalocyanines bearing thiophen-3-ylmethanol substituents: synthesis,characterization, aggregation behavior and antioxidant activity

The tetra α- or β-thiophene substituted metal and metal-free phthalocyanines (Pcs) M[Pc(α-OCH₂Thiopen)₄] and M[Pc(β-OCH₂Thiopen)₄] {(α-ThMet-MPc), (β-ThMet-MPc) [ThMet: Thiophene methoxy], M = Zn(II), Co(II) and, 2H} were synthesized from the corresponding 3’-(thiophen-3-ylmethoxy)phthalonitrile or 4’-(thiophen-3-ylmethoxy)phthalonitrile (ThMePN). The structural characterization, spectral, and antioxidant properties of a series of new Pcs were also presented. Both α- and β-substituted Pc complexes increased solubility in polar solvents, such as THF, DMF, and DMSO. FT-IR, ¹H-NMR, ¹³C-NMR, UV–vis, MALDI-TOF/MS spectral, and elemental analysis data were used to characterize the compounds. The aggregation behaviors of 3–8 were also investigated at different concentrations in THF. Antioxidant test methods, α,α-diphenyl-β-picrylhydrazyl radical scavenging activity, metal chelating activity, and reducing power, were used to determine the antioxidant activities. 6 showed very good ferrous ion chelating activity of 81 ± 1%. 6, 5, 4, and 3 showed better reducing power than trolox, ascorbic, acid and butylated hydroxytoluene, commercially used antioxidants.     

A systematic methodology to design silica templates: Silica microemulsion formulation and nanodroplet type and size estimation

A systematic study of the design and characterization of silica-microemulsion templates is presented. The ternary phase diagrams in micro-heterogeneous systems, by using a non-ionic surfactant (Brij 30) and different silica precursors (MTEOS, TEOS, PTEOS), have been drawn. Based on Khalweit diagrams, the phase inversion temperature was estimated as close to 315 K, for both alchil (TEOS) and aril (PTEOS) types of alcoxides. By correlating the information obtained from phase diagrams at room temperature with that of size effects revealed by VIS absorption molecular probes (bromthymol blue dye), the phase inversion point, i.e. the transition point from water-in-oil to oil-in-water microemulsion, was also clearly established as corresponding to R ∼ 1. Besides technically attractive features such as a wide variety of inorganic and hybrid nanomaterials, high specific surface and highly efficient applicative properties of the final materials, the approach of silica-microemulsion-based templates can be seen as a route towards the Green Chemistry concept.     

Synthesis,characterization and electrocatalytic performance of a dinuclear triazenidosilver(I) complex for hydrogen production

Our group has developed a series of molecular electrocatalysts for hydrogen generation based on triazenido–metal complexes (cobalt, copper, etc.). In this paper, we first present the electrocatalytic performance of a new dinuclear silver complex, [Ag₂(L)₂], formed by the reaction of the triazenido ligand 1‐[(2‐carboxymethyl)benzene]‐3‐[(2‐methoxy)benzene]triazene (HL) with AgNO₃. At room temperature, the silver complex shows photoluminescence at 653 nm. The electrocatalytic systems based on this silver complex can afford 106.57 and 1536.36 moles of hydrogen per mole of catalyst per hour from acetic acid at an overpotential (OP) of 991.6 mV and from a neutral aqueous buffer (pH = 7.0) at an OP of 837.6 mV, respectively. Electrochemical investigations show that both silver ion and triazenido ligand play a role in determining the catalytic activities of the electrocatalytic system.     

On Weak Solutions of Stochastic Differential Equations II

In the first part of this article a new method of proving existence of weak solutions to stochastic differential equations with continuous coefficients having at most linear growth was developed. In this second part, we show that the same method may be used even if the linear growth hypothesis is replaced with a suitable Lyapunov condition.     

Existence of nontrivial solutions for fractional Schrödinger equations with critical or supercritical growth

In this paper, we study the following fractional Schrödinger equation with critical or supercritical growth where 0 < s < 1, N > 2s, λ > 0, , , ( ? Δ)^s denotes the fractional Laplacian of order s and f is a continuous superlinear but subcritical function. Under some suitable conditions, we prove that the equation has a nontrivial solution for small λ > 0 by variational methods. Our main contribution is related to the fact that we are able to deal with the case .