Kinetic C<Subscript>(2)-H</Subscript> exchange study of<Emphasis Type="Italic">Cis</Emphasis>-[(en)<Subscript>2</Subscript>Co(HIm)(enH)]Br<Subscript>4</Subscript> by NMR spectroscopy: Evidence for the acidity of C<Subscript>(2)-H</Subscript> proton

C_(2)-H exchange incis-[(en)₂Co(HIm)(enH)]Br₄ (Im, imidazole; en, ethylenediamine) was studied over a pD range of 9.4 to 10.2 at 60°C where thecis-[(en)₂Co(Him)(enH)]⁴⁺ andcis-[(en)₂Co(HIm)(en)]³⁺ are the species present in significant concentrations.Cis-[(en)₂Co(HIm)(enH)]⁴⁺ has pK_a1 7.86 and pK_a2 9.82 with pK_a1 corresponding to coordinated enH ionization and pK_a2 to ImH ionization. The kinetic data may be interpreted in terms of an intramolecular H-D exchange mechanism, where the “dangling”-ND₂CH₂CH₂ND₂ group acts as a base to remove the imidazole C_(2)-H proton from the coordinated DIm moiety.     

Microstructural evolution of decagonal quasicrystal in the undercooled Al72Ni12Co16 alloy melts

The microstructure evolution of decagonal quasicrystals in Al₇₂Ni₁₂Co₁₆ alloy was investigated by the electromagnetic melting and cyclic superheating method. Single-phase decagonal quasicrystals have been obtained when the undercoolings were larger than 60 K. The decagonal quasicrystals formed at various undercoolings show different microstructural morphologies. Furthermore, grain refinement was found near the undercooling of 120 K. Based on current thermodynamic and dendrite growth theories, a dimensionless superheating parameter was adopted to explain the effect of processing conditions on the microstructure of Al₇₂Ni₁₂Co₁₆ alloy. The result indicate that the fine equiaxied microstructure of decagonal quasicrystal (D-phase) formed near on undercooling of 120 K originates from the break-up of dendrites.     

Degradative chain transfer in vinyl acetate polymerizations using toluene as solvent

In this work, we propose that retardation in vinyl acetate polymerization rate in the presence of toluene is due to degradative chain transfer. The transfer constant to toluene (C_trs) determined using the Mayo method is equal to 3.8 × 10^?3, which is remarkably similar to the value calculated from the rate data, assuming degradative chain transfer (2.7 × 10^?3). Simulations, including chain‐length‐dependent termination, were carried out to compare our degradative chain transfer model with experimental results. The conversion–time profiles showed excellent agreement between experiment and simulation. Good agreement was found for the M_n data as a function of conversion. The experimental and simulation data strongly support the postulate that degradative chain transfer is the dominant kinetic mechanism. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3620–3625, 2007     

Poly(L‐lysine) and clay nanocomposite with desired matrix secondary structure: Effects of polypeptide molecular weight

Nanocomposites (NC) were formed using cationic poly(L ‐lysine) (PLL), a semicrystalline polypeptide, that was reinforced by sodium montmorillonite (MMT) clay via solution intercalation technique. By varying solution conditions such as pH, temperature, and polypeptide concentration in the presence of clay platelets, the secondary structure of PLL was controllably altered into α‐helical, β‐sheet, and random coil. The high molecular weight polypeptide shows a strong propensity to fold into the β‐sheet structure when cast as films, irrespective of the initial secondary structure in solution. Nanocomposite local morphology confirms intercalated MMT platelets with PLL over a wide range of compositions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 239–252, 2007.     

Amorphous chalcogenide AgSbS2 films prepared by pulsed laser deposition

The pulsed laser deposition technique has been applied to prepare amorphous ternary AgSbS films. The films were prepared from AgSbS₂ bulk glass using a KrF excimer laser. The composition of prepared films according to the results of the energy dispersive X-ray analysis and the Rutherford backscattering was close to bulk one. Optical transmission and spectral dependence of the refractive index proved the good optical quality of the films. The Ar⁺ ion laser dot exposures of the films show a potential applicability of the films as a new type of optical recording material. PACS 78.66.Jg; 81.15.Fg; 81.40.Wx     

Comparative analysis of heterogeneous solid and soft materials by adsorption, NMR and thermally stimulated depolarisation current methods

Structural characterisation of such bio-objects as fibrinogen solution, yeast cells, wheat seeds and bone tissues has been done using two versions of cryoporometry based on the integral Gibbs-Thomson (IGT) equation for freezing point depression of pore liquids and the measurements by ¹H NMR spectroscopy (180-200 < T < 273 K) and the thermally stimulated depolarisation current (TSDC) method (90 < T < 273 K) of structured water. The IGT equation was solved using a self-consisting regularization procedure including the maximum entropy principle applied to the distribution function of pore size (PSD). Both methods give clear pictures of changes in the structural characteristics caused, e.g., by hydration and swelling of wheat seeds and yeast cells, coagulation and interaction of fibrinogen with solid nanoparticles in the aqueous media, and the human bone tissue disease.     

Creating, detecting and locating ultracold molecules in a surface trap

Ultracold molecules have been produced by photoassociation of Cs atoms trapped in a mirror magneto-optical trap. The molecules were detected by resonantly enhanced multi-photon ionization followed by time-of-flight mass spectroscopy. The time-of-flight ofatomic and molecular ions was investigated in the presence of a dc bias voltageapplied to the conducting mirror. This technique provides a new tool for determining the distance between the cold molecules and the mirror surface. This revised version was published online in August 2005 with a corrected cover date.     

Glass transitions and mixed phases in block SBS

Differential scanning calorimetry (DSC) does not allow for easy determination of the glass‐transition temperature (T_g) of the polystyrene (PS) block in styrene–butadiene–styrene (SBS) block copolymers. Modulated DSC (MDSC), which deconvolutes the standard DSC signal into reversing and nonreversing signals, was used to determine the (T_g) of both the polybutadiene (PB) and PS blocks in SBS. The T_g of the PB block was sharp, at ?92 °C, but that for the PS blocks was extremely broad, from ?60 to 125 °C with a maximum at 68 °C because of blending with PB. PS blocks were found only to exist in a mixed PS–PB phase. This concurred with the results from dynamic mechanical analysis. Annealing did not allow for a segregation of the PS blocks into a pure phase, but allowed for the segregation of the mixed phase into two mixed phases, one that was PB‐rich and the other that was PS‐rich. It is concluded that three phases coexist in SBS: PB, PB‐rich, and PS‐rich phases. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 276–279, 2005     

Optimization of in-vacuo template-stripped Pt surfaces via UHV STM

A recently demonstrated [1] in-vacuo template-stripping process is applied to the study of platinum films stripped from ultra-flat silicon-oxide surfaces. Template-stripped (TS) Pt surfaces, prepared with a range of post-deposition annealing times prior to being stripped from the templating surface in an ultra-high vacuum (UHV) environment, are examined by UHV scanning tunneling microscopy (STM). These studies reveal that without post-deposition annealing, TS Pt surfaces are largely made up of poorly-ordered, granular nanostructures undesirable for many applications. The post-deposition annealing treatments explored in the study result in the emergence and continuous growth of large smooth crystallites. Issues with crystallite orientation relative to the TS surface and artefacts arising as a result of the epoxy used in the template-stripping process are presented and discussed in relation to optimizing the template-stripping procedure for specific applications such as self-assembled monolayer (SAM) formation for molecular electronics. PACS 68.37.Ef; 68.47.De; 68.55.Jk; 81.05.Bx; 81.15.Ef     

Finite element modal solutions of planar photonic crystal fibers with rectangular air-holes

Modal solutions of planar photonic crystal waveguides with rectangular air-holes are presented by using a rigorous full-vectorial finite element-based approach. The effective indices, mode field profiles, spot-sizes, power confinements, modal hybridness, beat lengths and group velocity dispersions are shown for the fundamental and higher order modes of the quasi-TE and TM polarizations.