Conductivity relaxation in glass: Compositional contributions to non-exponentiality

That ionic conductivity in glass is a non-exponential process and has been known for many years. The amorphous structure of glass and hence a distribution of cation sites has often been thought to be the cause for the non-exponentiality. Almost completely unresearched, however, has been the effect of glass composition on the nature of the relaxation process. In this paper, we review the observations that have been made of the relationships between glass composition and the non-exponential character of the conductivity relaxation as well combine our recent wide composition range studies of sodium aluminoborate and lithium phosphate glasses to delineate the major features of the correlation. By examining glass compositions ranging from 0.02 to 60 mole% alkalioxide, it is observed that the rapid development of non-exponentiality within 1% Na₂O is accompanied by a similar rapid decrease in the average cation-cation separation distance, this being calculated using the composition and density. Other quantities such as the dc conductivity or activation energy are observed to vary too slowly with composition to produce a linear correlation with the extent of non-exponentiality as monitored in the parameter of the stretched exponentialkww function.     

Mixed C18 and C1 modification on an optical fiber for chromatographic sensing

An optical fiber-chromatographic sensor, aiming at simultaneous and selective response to multiple components following a chromatographic separation, is described. We report an improved approach for immobilization of octadecyl (C(18)) and methyl (C(1)) moieties as stationary phase on an optical fiber suitable as a sensing phase for organic solutes. By this approach, the stability and lifetime of the sensing layer as well as the detectability and retention behavior of the chromatographic sensor could be improved. Infrared spectroscopy was employed to confirm the presence of C(18) and C(1) moieties on the modified surface of the optical fiber. The chromatographic sensor was applied, with good sensitivity and chemical selectivity, to the simultaneous separation and detection of bromobenzene and toluene, using water as the mobile phase.     

Extending the scope of enantiomer separation by capillary supercritical fluid chromatography on immobilized polysiloxane-anchored permethyl-β-cyclodextrin (Chirasil-Dex)

Immobilized polysiloxane-anchored permethyl-β-cyclodextrin (Chirasil-Dex) with a cyclodextrin content of approximately 30 % by weight, previously employed as a versatile chiral stationary phase for the separation of enantiomers by GC, has been used for the separation of enantiomers by capillary supercritical fluid chromatography (SFC). A considerable number of racemates could be resolved, e.g. aromatic alcohols, amino alcohols (TFA derivatives), and underivatized acids. Many pharmaceutical compounds were among those analyzed, including several NSAIDs (e.g. ibuprofen and ketoprofen), a steroidal drug (nor-gestrel), a barbiturate (hexobarbital), and others. Among the racemates resolved were many which cannot be analyzed by GC owing to low volatility or decomposition at elevated temperatures. For two racemates, analysis temperature and mobile phase density were systematically varied to give constant analysis times or capacity factors k. Low temperatures (ca 60 °C) yielded the best separation in term of separation factor, α, or resolution, R_s, even though higher densities had to be used. In comparison with GC, capillary SFC was able to furnish higher separation factors and similar resolution. The applicability of capillary SFC for the analysis of mixtures of cyclodextrin derivatives, e.g. those used in the synthesis of Chirasil-Dex, was, furthermore, demonstrated.     

Synergies between micropreparative high-performance liquid chromatography and an instrumental optical biosensor

The recent development of an automated surface plasmon resonance technology for the measurement of biomolecular interactions (Pharmacia BIAcore) has provided new opportunities for the detection and analysis of protein-protein interactions. In the BIAcore, detection is based on changes in surface plasmon resonance which are monitored optically. Changes in surface plasmon resonance correspond to changes in surface concentration of macromolecules and can be monitored in real time.

We have found that the detection sensitivity obtainable with this technology (ng/ml concentrations of specific ligands are readily detectable for many applications) is complementary “in a bidirectional manner” to micropreparative HPLC. Thus micropreparative HPLC may be used to purify and characterise reagents for the biosensor, whilst the biosensor may be used to define chromatographic parameters such as elution conditions for affinity chromatography or serve as an affinity detector for fractions obtained during chromatographic purification.

Examples of such applications, including the potential of the biosensor to search for and monitor the purification of unknown ligands for which the target molecule has been identified, are shown. In particular, the use of the biosensor to monitor the purification of soluble epidermal growth factor receptor from A431 cell conditioned media is demonstrated.     

CIRCADIAN RHYTHM OF EXTRARETINAL PHOTOSENSITIVITY IN HATCHLING ALLIGATORS, ALLIGATOR MISSISSIPPIENSIS

Hatchling American alligators, Alligator mississippiensis , display a diel rhythm of extra-retinal (non-pineal) photosensitivity. There is a bimodal pattern in the threshold fluence rate required for initiating and effecting extra-retinally-mediated phototaclic responses. Significantly greater threshold fluence rates are required in the photophase than the scotophasc of a 12 h light: 12 h dark cycle. Under constant darkness there continues an endogenous, apparently circadian rhythm of extra-retinal photosensitivity. In all cases there is a significantly greater photosensitivity at lower temperatures.     

A New Method for the Construction of Macrolides Stereoselective Synthesis of (±)-Phoracantholide J. Preliminary communication

Starting from 5-chloro-2-pentanone ( 1 ) the naturally occurring 10-membered lactone phoracantholide J ( 8a ) has been synthesized as its racemate in a sequence of six steps (Scheme 2). Salient features of the syntheis include an internal selenium assisted acetal formation ( 4→5 ) and a stereoselective Claisen rearrangement ( 6→7→8 ). This general synthetic strategy offers an alternative approach towards the construction of macrocyclic lactones.     

Studies in mass spectrometry. IV—Fragmentation of aryltriflates. Substituent effects on [ArO]+ ion abundances: Looking for a best suited electron energy in the steady state approach. Experimental evidence for the ‘through bond’ stabilization of aryl cations by meta electron donor Substituents

The fragmentation patterns of 24 substituted phenyltrifluoromethanesulfonates has been determined by exact mass and metastable transition measurements. The influence of the ring substituent(s) on the abundance of the [ArO]+ ions has been investigated at low energies and a new standard parameter for plotting against Hammett's ó constants is proposed. The direct loss of CF₃SO₃ from the molecular ion of 3,5-(diisopropyl)-phenyl-, 3,5-(dicyclopropyl)phenyl- and 3,5-di(α-methylcyclopropyl)-phenyl-methanesulfonate, and further observations on the fragmentation processes of these compounds are consistent with M.O. calculations on the ‘through bond’ stabilization of the [Ar]+ σ state by meta electron donor substituents.