Pyrene-Doped Polyorganosiloxane Layers over Commercial Glass Fibers

Commercial glass fibers have been subjected to different activation treatments under neutral and acidic conditions to achieve different coating degrees when silanized with -aminopropyltriethoxisi lane (APES). A fluorescent sulfonamide (PSA) was formed between the amine residue and a fluorescent probe, pyrenesulfonyl chloride (PSC). Reflectance UV–Vis spectra of the pyrene-doped fibres show that pyrene is present in the form of preassociated dimers when the coating degree is low. Emission and excitation fluorescence spectra reveal the existence of a charge transfer ground-state complex with exciplex emission at 460–515 nm and absorption red-shifted with respect to the S₀ S₁ transition. Lifetime measurements yield three lifetimes, which are assigned to dimer, exciplex, and monomer emission. From the photophysical data it is concluded that the fibers with the highest silane content have an open structure with the highest fraction of isolated fluorescent moieties.     

On the Stability of the Quenched State in Mean-Field Spin-Glass Models

While the Gibbs states of spin-glass models have been noted to have an erratic dependence on temperature, one may expect the mean over the disorder to produce a continuously varying quenched state. The assumption of such continuity in temperature implies that in the infinite-volume limit the state is stable under a class of deformations of the Gibbs measure. The condition is satisfied by the Parisi Ansatz, along with an even broader stationarity property. The stability conditions have equivalent expressions as marginal additivity of the quenched free energy. Implications of the continuity assumption include constraints on the overlap distribution, which are expressed as the vanishing of the expectation value for an infinite collection of multi- overlap polynomials. The polynomials can be computed with the aid of a real-replica calculation in which the number of replicas is taken to zero.     

Deactivation of glass capillary columns by silylation. Part 1: Principles and basic technique

A deactivation procedure is described based on a published method using hexamethyldisilazane in the gas phase. In addition to unusually high inertia and thermostability, the method produces truly neutral columns which allow simultaneous analysis of moderately strong free acids and bases. The silylated columns show their full potential only with on-column injection. Preliminary experimental directions are given; more elaborate directions will become available after extended optimization work.     

The use of glass and fused silica open tubular columns for the separation of structural,configurational, and optical isomers by selective complexation GC: Sec-alcohols and ketones

The use of glass and fused silica open tubular columns for selective separation of structural, configurational, and optical isomers (enantiomers) of underivatized aliphatic alcohols and ketones by complexation gas chromatography on optically active metal chelates is described. The method represents a powerful analytical tool for the precise determination of diastereomeric (d.e.) and enantiomeric (e.e.) excesses in asymmetric syntheses and in natural product characterization. The direct screening of the enantiomeric composition and absolute configuration of terpinene-4-ol, the aggregation phermone of Polygraphus poligraphus (L), is described.     

Trace analysis of halocarbons in water; Direct aqueous injection with electron capture detection

Interest in monitoring halogenated organics in drinking water and natural surface and ground water in the low ppb range continues to grow. There is a tendency to include still more volatile halocarbons, the trace determination of which is known to be rather demanding. This prompted us to re-examine the feasibility of large-volume direct aqueous injection onto capillary columns, coupled with ECD. A primary problem was to avoid simultaneous elution of water with halocarbons, since water suppresses the ground current of the ECD. The following measures contributed to the solution of this problem. Apolar, extremely inert, columns are required to elute water completely, and even before very light halocarbons. Their coatings have to be far thicker (≈? 5 mUm) than commonly employed thick films since they must permit isothermal analysis at a column temperature around 100°C in order to ensure rapid and complete elution of water. Finally, it is essential that sampling be carried out on-column for two reasons: diffusion of water vapor in the injector, resulting in delayed elution, is then eliminated, and peak distortion during splitless injection is avoided. Although we now know that persilylated columns with immobilized coatings withstand routine water injections, more longterm experience is needed to provide detailed recommendations for the handling of these columns.     

Thermostable persilylated polar glass capillary columns by the ammonia-etching method

Static ammonia etching has been used to effect regular surface roughening of glass capillaries. Following such treatment, polar phases could be coated after persilylation with varioussilylation agents such as hexamethyl-, tetramethyldiphenyl-, and tetra- phenyldimethyldisilazane, respectively. This method produces columns of high thermostability, which is limited only by the maximum applicable temperature for the phase itself.     

氟代硼酸锂玻璃的分子动力学模拟

用分子动力学模拟方法,计算了氟代硼酸锂玻璃的电导率.研究的温度范围高于和近于玻璃转变温度,共模拟了七个体系,研究的成分大致覆盖了能形成玻璃的区域.所得极限电导率、活化能以及电导率随温度的变化与实验数据符合得相当好.以往的研究认为快离子传导的典型特征是仅有一种离子发生迁移,我们的模拟表明氟离子对电导也有较大贡献.用活化能数据可顺利解释这个三元系各体系的电导率相对高低问题.     

Dynamic Mechanical Relaxation in the Opaque and Transparent Poly(4-Methyl-1-Pentene) Films The glass transition zone

The thermomechanical properties of opaque and transparent polymer films of a solution of poly(4-methyl-1-pentene) (PMP) in cyclohexane and carbon tetrachloride obtained by casting on teflon and glass plates were investigated. The dynamic mechanical thermal analysis was applied in a frequency range from 0.01 to 100 Hz. The curves of loss tangent vs. temperature varied depending on the sample thermal history. The first part of these curves could relate to the backbone α relaxation into the unperturbed amorphous phase while the next relaxation could result from the backbone α relaxation into amorphous phase perturbed by the presence of the crystal domains. The Arrhenius plots of the first relaxation show a stronger curvature found in each of the transparent samples indicating strong dependency on specific volume. The second one in the case of transparent films and the first one for opaque samples might be approximate to straight lines. This revised version was published online in August 2006 with corrections to the Cover Date.     

Characteristic length of dynamic glass transition based on polymer/clay intercalated nanocomposites

The glass transition is an old physical problem. It has been accepted that there is a cooperatively rearranging region related to dynamic heterogeneity when temperature approaches the glass transition. However, there is no consensus with the characteristic length and the size of cooperatively rearranging region. This paper first employs the clay gallery in polymer/clay intercalated nanocomposites as a confined two-dimensional (2D) space to assess the characteristic length of dynamic glass transition. The five kinds of clays with different d-spacings were used to investigate the confinement effect. Theoretical calculation based on Donth's formula suggests that the characteristic lengths of polyol and polyol-based polyurethane are ∼3.20 and ∼1.45 nm, respectively. The experimental results agree with theoretical prediction using Donth's formula. The characteristic length varies with polymer types.     

Behavior of the effective fields for a regular ising model on the Cayley tree

A regular Ising model with nearest-neighbor interactions ofJ and–J(J>0) on a Cayley tree of coordination number 3 is investigated for the behavior of effective fields in a uniform external field. The effective fields show periodic and also aperiodic structures in the temperature-field plane. At absolute zero temperature, the equations determining effective fields are reduced to a nonlinear, one-dimensional, iterative equation. Arithmetic furcations of period and a screening of the furcations are observed.