Electron spin resonance study of copper(II) complexes with square pyramidal and compressed trigonal bipyramidal symmetries in different solvents at 295 K and 77 K

An electron spin resonance (ESR) study has been carried out on six copper(II) complexes. Two of these, Cu(den)(SCN)₂ and [Cu(den)(SCN)](ClO₄), have a square pyramidal CuN₄S coordination in the solid state while the remaining four complexes, Cu(pib)tu, Cu(bipy)tu, Cu(bipy) and Cu(bipyam), have compressed trigonal bipyramidal Cu(N₂S)N₂ Cu(N₂S)N₂, Cu(N₂Cl)N₂ and Cu(N₂I)N₂, respectively, type of coordination in the solid state. Excepting Cu(pib)tu, all complexes show characteristic isotropic fourline hyperfine structure in water, methanol, ethanol and dimethylformamide at 295 K. At 77 K, owing to the poor glass-forming ability of water, the spectral features are not properly resolved and are also not consistent with the lineshape requirements. Therefore, evaluation of spin Hamiltonian parameters is made from the frozen dimethylformamide spectra. Some interesting observations have been made. In highly viscous 2-methyl-benzoxazole, the spectral lineshape is considerably modified. Quantitative evaluation has been made of metal-ligand bonding and various contributions to linewidths.     

Synthesis and characterization of SPE membrane based on sulfonated FEP‐g‐acrylic acid by radiation induced graft copolymerization for PEM fuel cell

A Novel solid polymer electrolyte (SPE) membrane containing both ? COOH and ? SO₃H group has been prepared by simultaneous method of radiation grafting of acrylic acid onto FEP followed by sulfonation. The presence of weakly acidic acrylic acid controls the swelling in water while ? SO₃H group provides conductivity due to its strongly ionic characteristic. FEP‐g‐acrylic acid and its sulfonated derivatives were characterized by their properties. While the mechanical properties decreased, other properties such as ion exchange capacity (IEC), water uptake and ionic conductivity increased with increase in graft content. These properties further changed on sulfonation. Acrylic acid being weakly acidic in nature, conductivity values of the grafted membrane were quite low. However, introduction of strong ? SO₃H group resulted in conductivity closer to Nafion 117. Few sulfonated membranes have been tested with respect to H₂/O₂ fuel cell performance. Short‐term fuel cell test for 100 hr gave a stable performance. These membranes are less expensive compared to Nafion. Copyright © 2004 John Wiley & Sons, Ltd.     

Ultracentrifugation Method to Measure Water-Soluble Monomer Incorporation in Latex

Emulsion copolymerizations involving water-soluble functional monomers such as N-methylolacrylamide often result in the formation of water-soluble polymer that remains in the aqueous phase of the latex. A simple procedure is developed to determine the amount of water-soluble polymer in the aqueous phase of a high-solids latex using ultracentrifugation. Dilution of the latex with water is usually found necessary for good separation during ultracentrifugation. If the latex contains a surface-active species (surfactant) in amounts comparable to the amount of water-soluble polymer, calculation of the amount of water-soluble polymer in the serum of the original latex will require information about dilution dependent partitioning of the surfactant between the surface of the particles and the aqueous phase. This paper outlines a procedure that enables determination of the amount of water-soluble polymer in the aqueous phase of the original latex, by ultracentrifugation of the latex diluted to different concentrations. The procedure also gives the Henrys constant for the adsorption of the surfactant on the surface of the polymer particles in the latex.     

Singlet quenching of tetraphenylporphyrin and its metal derivatives by iron(III) coordination compounds

The quenching of fluorescence of the free-base tetraphenylporphyrin, H₂TPP, and its metal derivatives, MgTPP and ZnTPP by diverse iron(III) complexes, [Fe(CN)₆]³⁻, Fe(acac)₃, [Fe(mnt)₂]⁻, Fe(Salen)Cl, [Fe₄S₄(SPh)₄]²⁻·, FeTPPCl and [Fe(Cp)₂]⁺ has been studied both in homogeneous medium (CH₃CN) and micellar media, SDS., CTAB and Triton X-100. The quenching efficiencies are analysed in terms of diffusional encounters and it has been possible to separate static quenching components. The quenching constants are dependent on the nature of the ligating atoms around iron(III) and also on the extent of π-conjugation of the ligands. The quenching mechanism has been investigated using steady-state irradiation experiments. Evidence for oxidative quenching by iron(III) complexes was obtained, though the spin multiplicities of the excited electronic states of iron(III) complexes permit both energy and electron transfer mechanisms for quenching of the singlet excited state of the porphyrins.     

Hafnium oxide and zirconium oxide atomic layer deposition: initial precursor and potential side-reaction product pathways with H/Si(100)-2 x 1

Hybrid density functional calculations have been carried out using cluster models of the H/Si(100)-2 x 1 surface to investigate the mechanistic details of the initial surface reactions occurring in the atomic layer deposition of hafnium and zirconium oxides (HfO2 and ZrO2). Reaction pathways involving the metal precursors ZrCl4, Zr(CH3)4, HfCl4, and Hf(CH3)4 have been examined. Pathways leading to the formation of a Zr-Si or Hf-Si linkage show a significant sensitivity to the identity of the leaving group, with chloride loss reactions being both kinetically and thermodynamically less favorable than reactions leading to the loss of a methyl group. The energetics of the Zr(CH3)4 and Hf(CH3)4 reactions are similar with an overall exothermicity of 0.3-0.4 eV and a classical barrier height of 1.1-1.2 eV. For the reaction between H2O and the H/Si(100)-2 x 1 surface, the activation energy and overall reaction enthalpy are 1.6 and -0.8 eV, respectively. Due to contamination, trace amounts of H2O may be encountered by metal precursors, leading to the formation of minor species that can lead to unanticipated side-reaction pathways. Such gas-phase reactions between the halogenated and alkylated metal precursors and H2O are exothermic with small or no reaction barriers, allowing for the possibility of metal precursor hydroxylation before the H/Si surface is encountered. Of the contaminant surface reaction pathways, the most kinetically favorable corresponds to the surface -OH deposition. Interestingly, for the hydroxylated metal precursors, a unique reaction pathway resulting in the direct formation of Si-O-Zr and Si-O-Hf linkages has been identified and found to be the most thermodynamically stable pathway available, being exothermic by approximately 1.0 eV.     

Diversity-oriented synthesis of biaryl-containing medium rings using a one bead/one stock solution platform

Diversity-oriented synthesis of structurally complex and diverse small molecules can be used as the first step in a process to explore cellular and organismal pathways. The success of this process is likely going to be dependent on advances in the synthesis of small molecules having natural product-like structures in an efficient and stereoselective manner. The development, scope, and mechanism of the oxidation of organocuprates was investigated and exploited in the atropdiastereoselective synthesis of biaryl-containing medium rings (9-, 10-, and 11-membered rings). The methodology was performed on high-capacity, large polystyrene beads by metalating aryl bromides with i-PrBu(2)MgLi, followed by transmetalating with CuCN x 2LiBr and then oxidizing with 1,3-dinitrobenzene, and was used in a diversity-oriented synthesis of biaryl-containing medium rings (library total theoretical maximum 1412 members). The high capacity beads were arrayed into 384-well plates and, using a process optimized during the development of a one bead/one stock solution technology platform, converted into arrays of stock solutions, with each stock solution containing largely one compound. These stock solutions were used in numerous phenotypic and protein-binding assays. The process described outlines a pathway that we feel will contribute to a comprehensive and systematic chemical approach to exploring biology (chemical genetics).     

On the relation of generalized Valiron summability to Cesàro summability

A family (V _a ^k ) of summability methods, called generalized Valiron summability, is defined. The well-known summability methods (B_α,γ), (E _ρ, (T_α), (S _β) and (V _a) are members of this family. In §3 some properties of the (B _α,γ) and (V _a ^k ) transforms are established. Following Satz II of Faulhaber (1956) it is proved that the members of the (V _a ^k ) family are all equivalent for sequences of finite order. This paper is a good illustration of the use of generalized Boral summability. The following theorem is established: Theorem.If s _n (n ≥ 0) isa real sequence satisfying $$\mathop {lim}\limits_{ \in \to 0 + } \mathop {lim inf}\limits_{m \to \infty } \mathop {min}\limits_{m \leqslant n \leqslant m \in \sqrt m } \left( {\frac{{S_n - S_m }}{{m^p }}} \right) \geqslant 0(\rho \geqslant 0)$$ , and if s_n →s (V _a ^k ) thens _n → s (C, 2ρ).     

Intensity ratios of mesonic x-ray linesK_{\alpha _1 } , K_{\alpha _2 } andL_{\alpha _1 } , L_{\beta _2 }

Intensity ratios ofμ-mesonic x-rays in some heavy elements are discussed. Intensity ratios of the \(K_{\alpha _1 } /K_{\alpha _2 } \) and \(L_{\alpha _1 } /L_{\beta _2 } \) lines have been calculated for²⁰⁶Pb,²⁰⁹Bi and²³⁸U with relativistic wavefunctions and retardation effect. Though for a refined calculation, it is necessary to take into consideration several features that are peculiar to mesonic atoms, the present calculations have shown that the observed intensity ratios of mesonic x-rays are not anomalous.     

Analytical predictions of shapes of laminar diffusion flames in microgravity and earth gravity

Flame shape is an important observed characteristic of flames that can be used to scale flame properties such as heat release rates and radiation. Flame shape is affected by fuel type, oxygen levels in the oxidiser, inverse burning and gravity. The objective of this study is to understand the effect of high oxygen concentrations, inverse burning, and gravity on the predictions of flame shapes. Flame shapes are obtained from recent analytical models and compared with experimental data for a number of inverse and normal ethane flame configurations with varying oxygen concentrations in the oxidiser and under earth gravity and microgravity conditions. The Roper flame shape model was extended to predict the complete flame shapes of laminar gas jet normal and inverse diffusion flames on round burners. The Spalding model was extended to inverse diffusion flames. The results show that the extended Roper model results in reasonable predictions for all microgravity and earth gravity flames except for enhanced oxygen normal diffusion flames under earth gravity conditions. The results also show trends towards cooler flames in microgravity that are in line with past experimental observations. Some key characteristics of the predicted flame shapes and parameters needed to describe the flame shape using the extended Roper model are discussed.