Multiarm star triblock terpolymers via sequential double click reactions

Multiarm star triblock terpolymers were obtained by using two different click reactions sequentially: Cu(I) catalyzed azide–alkyne and Diels–Alder. The synthetic strategy is described as follows: (poly(methyl methacrylate))_n‐(polystyrene)_m‐poly(divinyl benzene)) ((PMMA)_n‐(PS)_m‐polyDVB) multiarm star diblock copolymer was first obtained from an azide–alkyne click reaction of (alkyne‐PS)_m‐polyDVB multiarm star polymer with α‐anthracene‐ω‐azide PMMA (anth‐PMMA‐N₃), followed by a Diels–Alder click reaction of the anthracene groups at the star periphery with α‐maleimide poly (tert‐butyl acrylate) (PtBA‐MI) or α‐maleimide poly(ethylene glycol) (PEG‐MI) leading to target (PtBA)_k‐(PMMA)_n‐(PS)_m‐polyDVB and (PEG)_p‐(PMMA)_n‐(PS)_m‐polyDVB multiarm star triblock terpolymers. The hydrodynamic diameter of individual multiarm star triblock terpolymers were measured by dynamic light scattering (DLS) to be ～24–27 nm in consistent with the atomic force microscopy (AFM) images on silicon substrates. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1557–1564, 2010     

Perturbation theory in a framework of iteration methods

In a previous paper [J. Phys. A 36 (2003) 11807], we introduced the ‘asymptotic iteration method’ for solving second-order homogeneous linear differential equations. In this Letter, we study perturbed problems in quantum mechanics and we use the method to find the coefficients in the perturbation series for the eigenvalues and eigenfunctions directly, without first solving the unperturbed problem.     

Syntheses,characterization of and studies on the electrochemical behaviour of ferrocenyl dithiophosphonates and 4-methoxyphenyl dithiophosphonates

Some 1,3-dithiadiphosphetane 2,4-disulfides (X₂P₂S₄, X: Fc, FcLR; X: CH₃O?C₆H₄?, LR) were allowed to react with alcohols to obtain dithiophosphonic acids (X(OR)PS₂H). These were converted to the corresponding ammonium salts. The salts were of the structures [Fc(OR)PS₂]^?[NH₄]⁺, R: 3-methyl-1-butyl- for I; 1-phenyl-1-propyl- for II; 3-pentyl- for III; 3-phenyl-1-propyl- for IV and [CH₃O?C₆H₄(OR)PS₂]^?[NH₄]⁺, R: 3-methyl-1-butyl- for V and 1-phenyl-1-propyl- for VI. To the best of our knowledge, all the compounds except V were prepared for the first time.

The compounds synthesized were characterized by elemental analysis, NMR (¹H, ¹³C, ³¹P), MS, FTIR, and Raman spectroscopies. Electrochemical behaviors of I–VI at disposable pencil graphite electrode (PGE) were investigated by using cyclic voltammetry (CV) and square-wave voltammetry (SWV). Adsorption and diffusion patterns of all the compounds on the PGE were also studied.

Two electroactive groups were identified in the compounds I–IV and only one in V and VI. The ferrocenyl groups of I-IV were oxidized at around 0.4 V. The same compounds display a second, more intense CV band at 0.8 V. The corresponding band for the compounds V–VI appears at around 0.6 V with a much weaker intensity. It is suggested that the ferrocenyl group introduced into the structures stabilizes the radical species formed as the product of the oxidation of the dithiophosphonato group.     

Butylene linked palladium N-heterocyclic carbene complexes: Synthesis and catalytic properties

New bis(NHC)-Pd complexes were synthesized and characterized by elemental analysis, ¹H NMR, ¹³C NMR, and IR spectroscopy. The reaction of Pd(OAc)₂ and bis(benzimidazolium) salts in DMSO gave the monomeric palladium complex in which the N-heterocyclic carbene was bound to the metal centre. The crystal and molecular structure of the cis-dibromo{1,1′-di[2,3,4,5,6-pentamethylbenzyl]-3,3′-butylenedibenzimidazol-2,2′-diylidene}-palladium(II) complex was determined by single-crystal X-ray diffraction. The activity of the Pd(II) complexes in the direct arylation of benzothiazole with arylbromides was investigated. A preliminary catalytic study showed that these bis(NHC)-Pd complexes were highly active in the direct arylation of benzothiazole with arylbromides.     

A theoretical investigation of the low energy conformers of the isomers glycine and methylcarbamic acid and their role in the interstellar medium

We have theoretically investigated the low energy conformers of neutral glycine (NH(2)CH(2)COOH) and its isomer methylcarbamic acid (CH(3)NHCOOH) in the gas phase. A total of 16 different levels of the theory, including CCSD(T), MP2 and B3LYP methods with various Pople and Dunning type basis sets with and without polarization and diffuse functions were used. We found eight low energy glycine conformers, where the heavy atoms in three have a planar backbone, and four low energy methylcarbamic acid conformers all with non-planar backbones. Interestingly at all levels of theory, we found that the most stable methylcarbamic acid conformer is significantly lower in energy than the lowest energy glycine conformer. The MP2 level and single point CCSD(T) calculations show the lowest energy methylcarbamic acid conformer to be between 31 to 37 kJ mol(-1) lower in energy than the lowest energy glycine conformer. These calculations suggest that methylcarbamic acid might serve as a precursor to glycine formation in the Interstellar Medium (ISM). We also report the theoretical harmonic vibrational frequencies, infrared intensities, moment of inertia, rotational constants and dipole moments for all of the conformers. In order to understand how glycine or methylcarbamic acid might be formed in the ISM, larger calculations which model glycine or its isomer interacting with several surrounding molecules, such as water, are needed. We demonstrate that B3LYP method should provide a reliable and computationally practical approach to modeling these larger systems.     

Broadband-cascaded four-wave mixing in a photonic crystal fiber around 1 μm

To our knowledge, efficient generation of broadband four-wave mixing cascades centered at 1 μm and spanning 600 nm is experimentally demonstrated for the first time. This frequency comb is generated from a two-tone seed with a maximum peak power of 25 W in a low-dispersion photonic crystal fiber. It consists of up to 44 new idler waves generated symmetrically around the seed.     

Non-linear vibrations of a simple-simple beam with a non-ideal support in between

A simply supported Euler-Bernoulli beam with an intermediate support is considered. Non-linear terms due to immovable end conditions leading to stretching of the beam are included in the equations of motion. The concept of non-ideal boundary conditions is applied to the beam problem. In accordance, the intermediate support is assumed to allow small deflections. An approximate analytical solution of the problem is found using the method of multiple scales, a perturbation technique. Ideal and non-ideal frequencies as well as frequency-response curves are contrasted.     

Synthesis of new bis-1,2,4-triazole derivatives

A series of new 1,2/1,3-bis[o-(N-methylidenamino-3-aryl-5-phenyl-4H-1,2,4-triazole-4-yl)phenoxy]ethane/propane derivatives 4 were prepared in good yields by treatment of 4-amino-3-aryl-5-phenyl-4H-1,2,4-triazoles 2 with certain bis-aldehydes 1.Compounds 4 were reduced with NaBH(4) to afford the corresponding 1,2/1,3-bis[o-(N-methylamino-3-aryl-5-phenyl-4H-1,2,4-triazole-4-yl)phenoxy]ethane/propane derivatives 5. All new compounds were characterized by IR, (1)H-NMR, (13)C-NMR and mass spectral data.     

Role of electrolyte pH on structural and magnetic properties of Co–Fe films

Co–Fe films were electrodeposited on polycrystalline Titanium substrates from the electrolytes with different pH levels. X-ray diffraction (XRD) was used to study the crystal structure of the films. The XRD patterns showed that the films grown at the pH levels of 3.70 and 3.30 have a mixed phase consisting of face-centred cubic (fcc) and body-centred cubic, while those grown at pH=2.90 have only fcc structure. It was observed that the film composition, by energy dispersive x-ray spectroscopy, contain around 88 at% Co and 12 at% Fe for all films investigated in this study. Morphological observations indicated that all films have grainy structure with the slight change of grain size depending on the electrolyte pH. Magnetoresistance measurements, made at room temperature, showed that all films exhibited anisotropic magnetoresistance, which is affected by the electrolyte pH. From the magnetic measurements made by vibrating sample magnetometer, the saturation magnetization increases as the electrolyte pH decreases. Furthermore, all films have in-plane easy-axis direction of magnetization.     

Contribution of electrolyte pH and deposition potentials to the magnetic anisotropy of electrodeposited nickel films

The influence of electrolyte pH and cathode potential on the magnetic properties of single layer Nickel films electrodeposited on polycrystalline titanium substrates was studied. The films were deposited at the electrolyte pH=3.5±0.1, 2.5±0.1 and 2.1±0.1 by varying the deposition potentials (?1.2, ?1.5 and ?1.8 V vs saturated calomel electrode, SCE) applied in continuous waveform. The structural analysis by X-ray diffraction revealed that the films have face-centred cubic structure. Results of the magnetic measurements obtained by vibrating sample magnetometer (VSM) indicated that the magnetic properties were affected by the electrolyte pH and the cathode potentials in terms of magnetic anisotropy. At the highest pH the films deposited at the lowest potential had in-plane magnetic anisotropy. As the electrolyte pH decreased from the high (pH=3.5±0.1) to low (pH=2.5±0.1), which is aided by increasing the potentials, resulted in an almost magnetic isotropy in the films. However, isotropic magnetic behaviour was observed for the film deposited at the low pH combined with the high potential (?1.8 V vs SCE). Magnetic thickness profile of the samples obtained by VSM revealed that the isotropic films have a smoother magnetic variation across the film from one edge than the anisotropic ones. This is also verified with a microscopic observation by an optical microscope and the surface of the isotropic films is observed to be smoother than that of the anisotropic ones. Furthermore, all films were found to have planar magnetic anisotropy irrespective of the pH’s and the potentials.