Visual sensing of saccharides promoted by resorcinol condensation products

[structure: see text] Heating aqueous DMSO solutions of five saccharides in the presence of 1-3 reveals that each receptor promotes solution colors characteristic for each sugar. New compound 3 allows the direct correlation of sugar concentration with visible region absorbance and/or fluorescence intensities.     

Liquid crystal elastomers: Synthesis and characterization

The synthesis is described of some acrylate based polymers containing both a mesogenic group (4-cyanophenyl benzoate) connected to the polymer backbone by a flexible spacer, and varying degrees of crosslinking, introduced by copolymerization. Optical and calorimetric techniques are used to determine the phase behavior, which is found to depend strongly on the crosslink density (and the flexible spacer length); though (nominally) a relatively high degree of crosslinking is possible without completely destroying the liquid crystal phase. Mechanical measurements in conjunction with supplementary analytical data, where available, are used to determine the efficiency of copolymerization at introducing intermolecular crosslinking. Some possible explanations for the unexpectedly low efficiency of this process are discussed. The properties of materials prepared in this fashion are compared briefly with some examples where crosslinking is introduced after polymerization; this latter process is seen to be rather more efficient.     

An evaluation of microextraction/capillary column gas chromatography for monitoring industrial outfalls

Microextraction and capillary-column gas chromatography techniques are applied to plant discharge streams for repetitive wastewater discharge permit analyses. This combination allows the analyst to reduce sample preparation since microextraction replaces both purge-and-trap for volatiles and microextraction for semi-volatiles. An additional advantage is the elimination of a concentration step, which is often a major contributor to low method recoveries. The overall procedure is shown to be more precise than purge-and-trap but slightly less precise than conventional extraction. The results of each method are shown to be equivalent.     

Evolution of molecular weight distributions in the catalytic chain transfer polymerization of methyl methacrylate up to high monomer conversions

The evolution of molecular weight distributions (MWDs) with monomer conversion in the catalytic chain transfer (CCT) polymerization of methyl methacrylate at 60 °C is investigated by simulation (via the program package PREDICI®) and experiment. A Co(III)‐based complex is used as the precursor for the CCT agent, which is formed in situ by initiator‐derived (2,2′‐azobisisobutyronitrile) radicals to yield the catalytically active Co(II) species. The small shifts seen in the MWD toward lower molecular weights with increasing monomer conversion are shown to be of the same order of magnitude as the associated changes in the MWD in non‐CCT controlled free‐radical polymerization, indicating that no significant change in the MWD with monomer conversion is associated with the CCT process. These results are compared to the evolution of MWDs in conventional chain transfer polymerizations with thiols as transfer agents. A clear shift toward higher molecular weights is seen with increasing monomer conversion, indicating disparate rates of thiol and monomer consumption. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3303–3312, 2000     

Influence of size,ellipticity and charge separation on the free energy of some aqueous bolaform electrolyte models

The free energy of some models of aqueous bolaform electrolytes have been calculated at the Debye-Hückel limiting law plus B ₂ level of approximation. The repulsive forces are modeled by hard spheres or hard ellipsoids. The charges are placed either at the center of the sphere or at the foci of the ellipsoid. Parameters were chosen to approximate the size and shape of sodium and calcium p-benzenedisufonate and sodium 4,4-biphenyldisulfonate. The results show that contrary to the standard explanations for the unusual properties of bolaform electrolytes, separating the charges has little effect on the excess free energy. It is also shown that changing from a sphere to an ellipse has little effect on the excess free energy. The most important determinates of the properties of these salts are the sizes of the ions. Agreement of the model calculations with experimental results is reasonable considering the simplicity of the models.     

The statistical overlap theory of chromatography using power law (fractal) statistics

The chromatographic dimensionality was recently proposed as a measure of retention time spacing based on a power law (fractal) distribution. Using this model, a statistical overlap theory (SOT) for chromatographic peaks is developed that estimates the number of peak maxima as a function of the chromatographic dimension, saturation and scale. Power law models exhibit a threshold region whereby below a critical saturation value no loss of peak maxima due to peak fusion occurs as saturation increases. At moderate saturation, behavior is similar to the random (Poisson) peak model. At still higher saturation, the power law model shows loss of peaks nearly independent of the scale and dimension of the model. The physicochemical meaning of the power law scale parameter is discussed and shown to be equal to the Boltzmann-weighted free energy of transfer over the scale limits. The scale is discussed. Small scale range (small β) is shown to generate more uniform chromatograms. Large scale range chromatograms (large β) are shown to give occasional large excursions of retention times; this is a property of power laws where "wild" behavior is noted to occasionally occur. Both cases are shown to be useful depending on the chromatographic saturation. A scale-invariant model of the SOT shows very simple relationships between the fraction of peak maxima and the saturation, peak width and number of theoretical plates. These equations provide much insight into separations which follow power law statistics.     

A highly reactive mononuclear non-heme manganese(IV)-oxo complex that can activate the strong C-H bonds of alkanes

A mononuclear non-heme manganese(IV)-oxo complex has been synthesized and characterized using various spectroscopic methods. The Mn(IV)-oxo complex shows high reactivity in oxidation reactions, such as C-H bond activation, oxidations of olefins, alcohols, sulfides, and aromatic compounds, and N-dealkylation. In C-H bond activation, the Mn(IV)-oxo complex can activate C-H bonds as strong as those in cyclohexane. It is proposed that C-H bond activation by the non-heme Mn(IV)-oxo complex does not occur via an oxygen-rebound mechanism. The electrophilic character of the non-heme Mn(IV)-oxo complex is demonstrated by a large negative ρ value of -4.4 in the oxidation of para-substituted thioanisoles.     

Diaxial diureido decalins as compact, efficient, and tunable anion transporters

Decalins bearing two axial -NHCONHAr substituents and an ester-linked alkyl side chain have been synthesized and studied as anion receptors and transporters. The design relates to steroid-based "cholapods" but is more compact and less intrinsically lipophilic. Transport rates depend on both NHAr and the alkyl side chain. High activities can be achieved; with optimal substitution, chloride-nitrate exchange across vesicle membranes is measurable at transporter/lipid ratios as low as 1:250,000.