Poly(pentamethylcyclopentasiloxane). I. Synthesis and characterization

We have discovered that pentamethylcyclopentasiloxane (D₅H) can be readily polymerized into poly(pentmethylcyclopentasiloxane) (PD₅) with a Pt (Karstedt) catalyst in the presence of water in bulk or in solution at 100 °C and that the product is a solid with extraordinary properties. The polymerization starts with the oxidation of the SiH groups by water into an intermediate containing SiOH groups (SiH + H₂O → SiOH + H₂), which is followed immediately by the condensation (2SiO → Si? O? Si) of D₅H rings into complex aggregates of cyclosiloxane moieties. According to Raman spectroscopy, an average of three of the five SiH functionalities are converted, and the final product contains only a negligible number of SiOH groups. The melting and glass‐transition temperatures of the monomer are exceptionally low: T_m,D5H = ?137.6 ± 1 and T_g,D5H = ?152 ± 2 °C. The polymer exhibits an unprecedented combination of properties: it is a stiff and brittle solid, is insoluble in common solvents, does not exhibit a melting endotherm but has an extremely low glass transition (T_g,PD5 = ?151 ± 0.5 °C), and is thermally stable up to at least 700 °C. Brillouin scattering indicates very slow variation of the relaxation time with temperature, a property characteristic of strong glass‐forming systems such as silica glass. This characteristic may account for the unique combination of properties of the new polymer: an extremely low glass‐transition temperature combined with solidlike properties even at ambient temperature (more than twice its glass‐transition temperature). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1285–1292, 2002     

Determination of traces of palladium by adsorptive stripping voltammetry of the dimethylglyoxime complex

Preconcentration is achieved by adsorption of a palladium-dimethylglyoxime complex on a hanging mercury drop electrode. Optimal conditions area stirred acetate buffer solution (pH 5.15) containing 2 × 10^?4 M dimethylglyoxime and an accumulation potential of —0.20 V. The height of the stripping peak in a negative-going linear scan is linearly dependent on palladium concentration and preconcentration time (over the ranges 0–16 μg l^?1 and 0–300 s, respectively). For a 10-min preconcentration time, the detection limit is 20 ng l^?1 (2.1 × 10^?10 M). Possible interferences by other trace metals are investigated. Palladium added to seawater samples was easily quantified.     

Preparation, structures, and haptotropic rearrangement of novel dinuclear ruthenium complexes, (μ2,η:η-guaiazulene)Ru2(CO)4(CNR)

Novel isonitrile derivatives of a diruthenium carbonyl complex, (μ₂,η³:η⁵-guaiazulene)Ru₂(CO)₅ (2), were synthesized by substitution of a CO ligand by an isonitrile, and were subjected to studies on thermal and photochemical haptotropic interconversion. Treatment of 2 (a 45:55 mixture of two haptotropic isomers, 2-A and 2-B) with RNC at room temperature resulted in coordination of RNC and alternation of the coordination mode of the guaiazulene ligand to form (μ₂,η¹:η⁵-guaiazulene)Ru₂(CO)₅(CNR), 5d–5f, [5d; R=^tBu, 5e; 2,4,6-Me₃C₆H₂, or 5f; 2,6-ⁱPr₂C₆H₃] in moderate to good yields. Thermal dissociation of a CO ligand from 5 at 60 °C resulted in quantitative formation of a desirable isonitrile analogue of 2, (μ₂,η³:η⁵-guaiazulene)Ru₂(CO)₄(CNR), 4d–4f, [4d; R=^tBu, 4e; 2,4,6-Me₃C₆H₂, or 4f; 2,6-ⁱPr₂C₆H₃], as a 1:1 mixture of the two haptotropic isomers. A direct synthetic route from 2 to 4d–4f was alternatively discovered; treatment of 2 with one equivalent of RNC at 60 °C gave 4d–4f in moderate yields. All of the new compounds were characterized by spectroscopy, and structures of 5d (R=^tBu) and 4d-A (R=^tBu) were determined by crystallography. Thermal and photochemical interconversion between the two haptotropic isomers of 4d–4f revealed that the isomer ratios in the thermal equilibrium and in the photostatic state were in the range of 48:52–54:46.     

Angular distributions of fast electrons, ions, and Bremsstrahlung x/gamma-rays in intense laser interaction with solid targets

We study the angular distributions of fast electrons, ions, and bremsstrahlung x/ gamma-rays generated during the interaction of an ultrashort intense laser pulse with solid targets. A relation is found on the angular directions for fast electrons and ions as a function of the particle's kinetic energy, experienced Coulomb potential changes, and the incident angle of the laser pulse. It is valid independent of the acceleration mechanisms and the polarization of the laser pulse, as confirmed by particle-in-cell simulations. The angular distribution of bremsstrahlung x/gamma-rays is presented to show explicitly its correlation with the corresponding angular distributions of electrons.     

Dry tin dioxide hollow microshells and extreme ultraviolet radiation induced by CO2 laser illumination

Low-density tin dioxide (SnO2) is required for radiating monochromatic extreme ultraviolet (EUV) light with low debris and high conversion efficiency from a laser. In this paper, tin dioxide nanoparticle hollow microcapsules were successfully fabricated by a layer-by-layer template technique. The obtained capsules have a rougher surface (30 nm in rms) compared to the freshly prepared polyelectrolyte capsules. Based on the X-ray diffraction (XRD) results, the tin dioxide nanoparticles well maintained their size after they were assembled on the capsules' surfaces. In order to remove the polymer template, a heat treatment was introduced, and after the heat treatment the capsule sizes shrank about 71% (the average size was from 4.9 to 3.5 mum), and the obtained capsules maintained their round shape after water evaporation. The narrowest bandwidth at the 13.5 nm emission in the EUV region was observed when the capsules were irradiated by a CO2 laser with an intensity of 2.9 x 10(10) W/cm (2).     

Water-mediated correlations in DNA-enzyme interactions

In this letter we consider dipole-mediated correlations between DNA and enzymes in the context of their water environment. Such correlations emerge from electric dipole-dipole interactions between aromatic ring structures in DNA and in enzymes. We show that there are matching collective modes between DNA and enzyme dipole fields, and that a dynamic time-averaged polarization vanishes in the water dipole field only if either DNA, enzyme, or both are absent from the sample. This persistent field may serve as the electromagnetic image that, in popular colloquialisms about DNA biochemistry, allows enzymes to “scan” or “read” the double helix. Topologically nontrivial configurations in the coherent ground state requiring clamplike enzyme behavior on the DNA may stem, ultimately, from spontaneously broken gauge symmetries.     

Decrease of superparamagnetic fraction at room temperature in ultrafine CoFe2O4 particles by Ag doping

Co_1???x Ag _x Fe₂O₄ nanoparticles have been prepared by the combustion route. The average crystallite sizes for compositions with x = 0 and 0.2 are found to be 36 and 33 nm respectively from the XRD line broadening. Compared to the pure CoFe₂O₄, Ag-doping reduces the intrinsic magnetization values (M, M _r), but enhances coercivity (H _c). Mössbauer spectra show two sextets, indicating occupancies of tetrahedral and octahedral sites by Fe^3?+?. Hyperfine fields of 505 and 477 kOe in pure CoFe₂O₄ have been found for octahedral and tetrahedral sites respectively at liquid nitrogen temperature. The hyperfine field decreases with Ag-doping which also corroborates the magnetization studies. EPR study confirms the room temperature ferromagnetic behavior for Co_1???x Ag _x Fe₂O₄ (x = 0.2). The room temperature Mössbauer studies on x?=?0.0 and 0.2 show the ferromagnetic sextets (95%) along with superparamagnetic doublet (5%). However, x = 0.6 sample shows the ferromagnetic sextets only at room temperature. Highly Ag doped samples could be useful for the fabrication of the high-density magnetic materials as well as magnetic drug delivery.     

Magnetic and Mössbauer studies on nanocrystalline Co1−x Li x Fe2O4 (x = 0, 0.2)

Ultrafine particles of Co_1???x Li _x Fe₂O₄ (x?= 0, 0.2) samples are prepared by glycine–nitrate combustion route. X-ray diffraction and transmission electron microscopy studies show that the samples have cubic spinel structure and average crystallite sizes of x?= 0 and 0.2 are 36 and 44 nm respectively. Vibrating sample magnetometer studies revealed the ferromagnetic nature of the samples. Li-doped CoFe₂O₄ sample showed higher values of coercive field, remanent magnetization and saturation magnetization compared to pure CoF₂O₄ indicating the enhancement of magnetic interactions. Mössbauer spectra at 77 K exhibited two broad sextets indicating that Fe^3?+? ions occupy both tetrahedral and octahedral sites. From these studies, it is concluded that Co_1???x Li _x Fe₂O₄ (x?= 0, 0.2) samples exhibit an inverse spinel structure. At room temperature, two sextets are superimposed on a very broad non-Lorentzian background indicating the presence of superparamgnetic fraction in agreement with the microscopic observations.     

Magnetic-dipole vortex generation by propagation of ultraintense and ultrashort laser pulses in moderate-density plasmas

A magnetic-dipole vortex is generated in the behind of an ultraintense and ultrashort laser pulse in a near critical density plasma. The vortex is self-sustained by its magnetic field pressure which expels background electrons, and resulting sheath field accelerates electrons to drive high amplitude electric current inside the vortex. The electron energy spectra shows nonthermal distribution with relatively high energy. The vortex is stable for a long period since it is in the electromagnetic equilibrium, whose structure and characteristics are explained by a simple analytical model.     

Molecular weight distribution formed during free‐radical polymerization in the presence of polyfunctional chain transfer agents

Free‐radical polymerization of styrene was carried out in the presence of chain transfer agents (CTAs) with functionality, f = 1–4. The size exclusion chromatography (SEC) with an ultraviolet absorption detector (UV) was used to measure the molecular weight distribution (MWD). A Monte Carlo simulation method proposed earlier was used to investigate the experimental results. In this simulation method, one can observe the structure of each polymer molecule directly, and very detailed information can be obtained in a straightforward manner, including the elution curve of SEC. It was found that up to the functionality f = 3, the equal reactivity model that assumes the reactivity of all functional groups in a CTA is equal agrees reasonably well with the experimental results. However, with f = 4, the reactivity of the fourth functional group seems to decrease and the substitution effects may need to be accounted for to fine control the formed branched structure. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1267–1275, 1999