Studies on some radical transfer reactions by entrapping the radicals as polymer endgroups. III. Reaction of ȮH radical with halide ions

The reactions of OH radical with Cl^?, Br^?, I^?, and F^? ions have been studied by entrapping the product radicals as polymer endgroup which have been detected and estimated by the sensitive dye partition technique. The rate constants of the reactions with Br^?, Cl^?, and F^? ions have been determined to be 1.51 × 10⁹, 1.32 × 10⁹, and 0.92 × 10⁹ L mol^?1 s^?1, respectively at 25°C and pH 1.00. Oxidation of I^? ions liberates I, which inhibits the polymerization and the reaction could not be followed by polymer endgroup analysis. The observed order of reactivity Br^? > Cl^? > F^? is in accordance with the electron affinities of the halide ions. The acidity of the reaction medium has a strong influence on the rate of reaction. With Br^? ions, the rate constant of the reaction falls from 1.51 × 10⁹ to 0.75 × 10⁹ L mol^?1 s^?1 at 25°C as the pH is raised from 1.0 to 2.8. The method is simple and accurate and can be applied to study very reactive radicals.     

Kinetics of the displacement of aqua ligands from cis-diaqua(ethylenediamine)-platinum(II)perchlorate by adenosine 5′-monophosphate in aqueous medium

The kinetics of the interaction of adenosine 5-monophosphate (5-AMP) with cis-[Pt(en)(H₂O)₂]²⁺ have been studied spectrophotometrically as a function of [Pt(en)(H₂O)₂]²⁺, [5-AMP] and temperature at pH 4.0, where the substrate complex exists predominantly as the diaqua species. Both N1 and N7 donor sites of 5-AMP are active for coordination to Pt at this pH. Base stacking and metal-induced macrochelate formation of 5-AMP plays a vital role in determining the concentration limit of 5-AMP during kinetics. Substitution occurs in two consecutive steps; both dependent on the 5-AMP concentration. Activation parameters for both steps have been calculated. The low H ₁ (42.76 ± 1.64 kJ mol^–1) and large negative values of S ₁ (–112.1 ± 5.1 J K^–1 mol^–1) as well as H ₂ (58.1 ± 1.4 kJ mol^–1) and S ₂ (–84.2 ± 4.4 J K^–1 mol^–1) indicate associative modes of activation for both ligand substitution processes in the two consecutive steps.     

Irradiation-induced magnetism in carbon nanostructures

Nitrogen (15N) and carbon (12C) ion implantations with implant energy of 100 keV for different doses were performed on nanosized diamond (ND) particles. Magnetic measurements on the doped ND show ferromagnetic hysteresis behavior at room temperature. The saturation magnetization (M(s)) in the case of 15N implanted samples was found to be higher compared to the 12C implanted samples for dose sizes greater than 10(14) cm(-2). The role of structural modification or defects along with the carbon-nitrogen (C-N) bonding states for the observed enhanced ferromagnetic ordering in 15N doped samples is explained on the basis of x-ray photoelectron spectroscopy measurements.     

Wet-chemical templateless assembly of metal nanowires from nanoparticles

We describe a new, simple, room-temperature wet-chemical approach for assembling Au and Ag nanoparticles into nanowire networks, without the use of lithographic templates. Five to 35 nm-diameter nanowires passivated with a thin organic layer were synthesized by mechanically agitating a biphasic liquid mixture of an aqueous hydrosol containing the nanoparticles, and toluene. Nanowire structure and surface chemistry are discussed based on electron microscopy, UV-visible spectroscopy and thermogravimetric analyses.     

Superluminal neutrinos at OPERA confront pion decay kinematics

Violation of Lorentz invariance (VLI) has been suggested as an explanation of the superluminal velocities of muon neutrinos reported by OPERA. In this Letter, we show that the amount of VLI required to explain this result poses severe difficulties with the kinematics of the pion decay, extending its lifetime and reducing the momentum carried away by the neutrinos. We show that the OPERA experiment limits α=(ν(ν)-c)/c<4×10(-6). We then take recourse to cosmic-ray data on the spectrum of muons and neutrinos generated in Earth's atmosphere to provide a stronger bound on VLI: (ν-c)/c<10(-12).     

Templateless room-temperature assembly of nanowire networks from nanoparticles

We demonstrate a new, room-temperature approach to assemble two-dimensional and three-dimensional networks of gold nanowires by agitating nanoparticles in a toluene-aqueous mixture, without the use of templates. The nanowires have a uniform diameter of about 5 nm and consist of coalesced face-centered cubic nanocrystals. Toluene molecules passivate the gold surfaces during nanoparticle coalescence, rendering the nanowires hydrophobic and enabling their transfer into the toluene layer. Such templateless low-temperature assembly of mesostructures from nanoscale building blocks open up new possibilities for creating porous self-supporting nanocatalysts, nanowires for device interconnection, and low-density high-strength nanofillers for composites.     

Kinetics of substitution of aqua ligands from cis-diaqua(ethylenediamine)platinum(II) perchlorate by DL-penicillamine in aqueous medium

The kinetics of the interaction of DL-penicillamine with [Pt(en)(H₂O)₂]²⁺ have been studied spectrophotometrically as a function of [Pt(en)(H₂O)₂]²⁺, [DL-penicillamine] and temperature at pH 4.0. The reaction proceeds via rapid outer sphere association complex formation, followed by two slow consecutive steps. The first is the conversion of the aforementioned complex into the inner sphere complex and the second is the slower chelation step whereby another aqua ligand is replaced. The association equilibrium constant (K _E) for the outer sphere complex formation has been evaluated together with rate constants for the two subsequent steps. Activation parameters have been calculated for both steps using the Eyring equation (H ₁ = 46.5 ± 5.0 kJ mol^–1, S ₁ = – 143.0 ± 15.0 J K^–1 mol^–1, H ₂ = 44.3 ± 1.3 kJ mol^–1, S ₂ = –189.0 ± 4.2 J K^–1 mol^–1). The low enthalpy of activation and large negative entropy of activation values indicate an associative mode of activation for both aqua ligand substitution processes.     

Studies on some radical transfer reactions by entrapping the radicals as polymer end groups. I. Reaction of hydroxyl radicals with amines

The reaction of OH radicals with a number of amines has been studied by entrapping the resultant radicals as polymer end groups which have been detected and estimated by the sensitive dye partition technique. Expressions have been developed relating the average amounts of end groups per polymer molecule to the rate constant of the radical transfer reaction, the rate constants determined for reaction with n-butyl, n-hexyl, and n-octyl amine being 1.00 × 10¹⁰, 1.31 × 10¹⁰, and 1.46 × 10¹⁰ mol^?1 L s^?1, respectively, at 25°C. The order of reactivity for amines of different classes has been found to be as primary < secondary > tertiary, the rate constants for reaction with n-butyl, dibutyl, and tributyl amine being 1.00 × 10¹⁰, 1.81 × 10¹⁰, and 1.67 × 10¹⁰ mol^?1 L s^?1, respectively, at 25°C. The change in the reactivity of the amine with chain length and amine class has been explained by activation and deactivation of the CH₂ group from which H abstraction by OH radicals occurs, respectively, by the alkyl group and by the protonated amino nitrogen under the acidic condition of the medium. Between pH 1.00 and 2.17, the rate of the reaction with n-butyl amine remains practically unchanged, but from pH 2.20 to 2.72 the rate constant increases with increasing pH, indicating that deprotonation of the positively charged nitrogen starts at about pH 2.20. The method is simple and accurate and can be applied to detect and estimate very reactive radicals.