A novel tridentate nitrogen donor as ligand in copper catalyzed ATRP of methyl methacrylate

A tridentate ligand, BPIEP: 2,6‐bis[1‐(2,6‐diisopropyl phenylimino) ethyl] pyridine, having central pyridine unit and two peripheral imine coordination sites was effectively employed in controlled/“living” radical polymerization of MMA at 90°C in toluene as solvent, Cu^IBr as catalyst, and ethyl‐2‐bromoisobutyrate (EBiB) as initiator resulting in well‐defined polymers with polydispersities M_w/M_n ≤ 1.23. The rate of polymerization follows first‐order kinetics, k_app = 3.4 × 10^?5 s^?1, indicating the presence of low radical concentration ([P*] ≤ 10^?8) throughout the reaction. The polymerization rate attains a maximum at a ligand‐to‐metal ratio of 2:1 in toluene at 90°C. The solvent concentration (v/v, with respect to monomer) has a significant effect on the polymerization kinetics. The polymerization is faster in polar solvents like, diphenylether, and anisole, as compared to toluene. Increasing the monomer concentration in toluene resulted in a better control of polymerization. The molecular weights (M_n,SEC) increased linearly with conversion and were found to be higher than predicted molecular (M_n,Cal). However, the polydispersity remained narrow, i.e., ≤1.23. The initiator efficiency at lower monomer concentration approaches a value of 0.7 in 110 min as compared to 0.5 in 330 min at higher monomer concentration. The aging of the copper salt complexed with BPIEP had a beneficial effect and resulted in polymers with narrow polydispersitities and higher conversion. PMMA obtained at room temperature in toluene (33%, v/v) gave PDI of 1.22 (M_n = 8500) in 48 h whereas, at 50°C the PDI is 1.18 (M_n = 10,300), which is achieved in 23 h. The plot of lnk_app versus 1/T gave an apparent activation energy of polymerization as (ΔE^≠_app) 58.29 KJ/mol and enthalpy of equilibrium (ΔH⁰_eq) to 28.8 KJ/mol. Reverse ATRP of MMA was successfully performed using AIBN in bulk as well as solution. The controlled nature of the polymerization reaction was established through kinetic studies and chain extension experiments. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4996–5008, 2005     

Iridodials: enantiospecific synthesis and stereochemical assignment of the pheromone for the golden-eyed lacewing, Chrysopa oculata

1R,2S,5R,8R; 1R,2S,5R,8S; 1S,2S,5R,8R; and 1S,2S,5R,8S-Iridodials have been prepared in five steps from 4aS,7S,7aR and 4aS,7S,7aS-nepetalactones, major components of catnip oil. 1R,2S,5R,8R-Iridodial has been identified as a male-produced male-aggregation pheromone for Chrysopa oculata, the first pheromone of any kind identified for lacewings.     

Synthesis of O,O Ethane Bridged Bis-copper(II) Macrocycles. Selective Enzyme Model for Catecholase Activity

New mononuclear and dinuclear complexes [3-hydroxyethyl-1,3,5,8,11pentaazacyclotridecane]copper(II) (1)/nickel(II) (2) perchlorate and O,O ethane bridged bis-copper(II) (3)/nickel(II) (4) macrocycles have been synthesized and characterized by various spectroscopic techniques, viz. i.r., n.m.r., e.p.r., u.v.–vis. and conductance measurements. Spectral data and conductance measurements reveal that all the complexes are consistent with square-planar geometry and are ionic in nature. The catalytic activity of the dinuclear Cu(II) complex (3) in the presence of pyrocatechol was determined spectrometrically by monitoring the increase of the o-benzoquinone characteristic absorption band at 25,000 cm⁻¹ with respect to time in DMF saturated with molecular oxygen. The kinetic parameters V_max (2.8×10⁻³ M s⁻¹) and K_M (1.4×10⁻³ mm) have been determined by Michaelis–Menten method. Electrochemistry of the dinuclear Cu(II) complex has been studied in the presence of molecular oxygen with pyrocatechol and without pyrocatechol at a scan rate of 0.1 V s⁻¹ by cyclic voltammetry. On addition of pyrocatechol, complex shows a shift in E_pc, E_pa and E_1/2 values indicating the oxidation of substrate (pyrocatechol).     

Diffusion behavior of pharmaceutical O/W microemulsions studied by dynamic light scattering

Dynamic light scattering experiments have been performed at various concentrations, of pharmaceutical oil-in-water microemulsions consisting of Eutanol G as oil, a blend of a high (Tagat O2) and a low (Poloxamer 331) hydrophilic–lipophilic balance surfactant, and a hydrophilic phase (propylene glycol/water). We probe the dynamics of these microemulsions by dynamic light scattering. In the measured concentration range, two modes of relaxation were observed. The faster decaying mode is ascribed classically to the collective diffusion D _c (total droplet number density fluctuation). We show that the slow mode is also diffusive and suggest that its possible origin is the relaxation of polydispersity fluctuations. The diffusion coefficient associated with this mode is then the self-diffusion D _s of the droplets. It was found that D _c and D _s had opposite volume fractions of oil plus surfactants (ϕ) dependence and a common limiting value D ₀ for ϕ=0. Average hydrodynamic radius (R _h=10.5 nm) of droplets was calculated from D ₀. R _h is supposed to compose the inner core, a surfactant film including possible solvent molecules, which migrate with the droplet. The concentration dependence of diffusion coefficients reflects the effect of hard sphere and the supplementary repulsive interactions which arises due to loss of entropy, when absorbed chains of surfactant intermingle on the close approach of the two droplets. This mechanism could also explain the observed stability of our systems. The estimated extent of polydispersity is 0.22 from the amplitude of slower decaying mode. The polydispersity in microemulsion systems is dynamic in origin. Results indicate that the time scale for local polydispersity fluctuations is at least three orders of magnitude longer than the estimated time between droplet collisions.     

Dynamic light-scattering analysis of the electrostatic interaction of hexahistidine-tagged cytochrome P450 enzyme with semiconductor quantum dots.

Currently, there is great interest in the development of methods suitable for determining the stoichiometry of biomolecules attached to nanoparticles. We describe the use of the dynamic light-scattering technique (DLS) to determine the stoichiometry of the protein cytochrome P450(BSbeta) attached to CdS and CdSe quantum dots (QDs). The enzyme-conjugated QDs have different diffusion characteristics compared to the QD and enzyme precursors, expressed in their size, scattering intensity as well as zeta-potential values. The significant enhancement of the scattering intensity of QDs observed upon conjugation with the P450(BSbeta) due to the refractive-index increment and the systematic variation in zeta potential resulting from charge neutralization of the anionic QDs by the cationic histidine-tagged P450(BSbeta) have been used for stoichiometry determination.     

Crystallographic evidence of hexacoordination at phosphorus via intramolecular coordination of donor groups on phosphane and phosphane sulphide

The X-ray structure analysis of bis(8-dimethylamino-l-naphthyl)phenylphosphane (3) and of the corresponding sulphide 4 has revealed hexacoordination at phosphorus in both cases, the N … P separations being less than the sum of the van der Waal radii. Furthermore, in both cases the overall geometry corresponds to a distorted bicapped tetrahedron. The optimum geometry calculated for 4 via the program developed by Autodesk (MM + method) suggests that the structure of the molecule is a function not only of steric requirements but also of electronic effects.     

An unusual, mild and convenient one-pot two-step access to (E)-stilbenes from hydroxy-substituted benzaldehydes and phenylacetic acids under microwave activation: a new facet of the classical Perkin reaction

A mild and convenient one-pot two-step synthesis of hydroxystilbenes with trans selectivity has been developed through a modified Perkin reaction between benzaldehydes and phenylacetic acids bearing 4- or 2-hydroxy substitution at the aromatic ring, in the presence of piperidine-methylimidazole and polyethylene glycol under microwave irradiation. The observation of a simultaneous condensation-decarboxylation leading to the unusual formation of hydroxystilbenes in lieu of α-phenylcinnamic acid reveals an interesting facet to the classical Perkin reaction. The developed protocol provides a green alternative to the prevalent methods employing a toxic decarboxylating agent in the form of quinoline/Cu salt, and the requirement for harsh protection-deprotection steps for the synthesis of hydroxylated stilbenes.     

Synthesis, spectra and biomimetic properties of copper(II)-copper(II) and copper(II)-zinc(II) binuclear complexes with CuN5 chromophores

X-band electron spin resonance (ESR) and UV-vis spectra of a homobinuclear [(Bipy)2Cu-E-Im-Cu(Bipy)2](BF4)3 and a heterobinuclear [(Bipy)2Cu-E-Im-Zn(Bipy)2](BF4)3 complexes, E-Im=2-ethylimidazolate ion have been described as possible models for superoxide dismutase (SOD). Magnetic moment and ESR spectral measurements of the homobinuclear complex have shown an antiferromagnetic exchange interaction. From pH-dependent ESR and UV-vis spectral measurements studies, these complexes have been found to be stable over 8.5-10.5 pH range. These complexes catalyze the dismutation of superoxide (O2-) at biological pH. All the observations indicate that these complexes act as good possible models for superoxide dismutase.     

Biomimetic reduction of nimesulide with NaBH4 catalyzed by metalloporphyrins

The biomimetic reduction of anti-inflammatory drug, nimesulide (1) with sodium borohydride catalyzed by 5,10,15,20-tetraarylporphyrinatoiron(III) chlorides [TAPFe(III)Cl] has been studied in organic solvents under anaerobic and aerobic conditions.