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Efficiency and resolution in capillary liquid chromatography (LC) can be significantly affected by extra-column band broadening, especially for isocratic separations. This is particularly a concern in evaluating column bed structure using non-retained test compounds. The band broadening due to an injector supplied with a commercially available capillary LC system was characterized from experimental measurements. The extra-column variance from the injection valve was found to have an extra-column contribution independent of the injection volume, showing an exponential dependence on flow rate. The overall extra-column variance from the injection valve was found to vary from 34 to 23 nL. A new mathematical model was derived that explains this exponential contribution of extra-column variance on chromatographic performance. The chromatographic efficiency was compromised by ∼130% for a non-retained analyte because of injection valve dead volume. The measured chromatographic efficiency was greatly improved when a new nano-flow pumping system with integrated injection valve was used.

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New monolithic reversed-phase liquid chromatography (RPLC) stationary phases based on single multi-acrylate/methacrylate-containing monomers [i.e., 1,12-dodecanediol dimethacrylate (1,12-DoDDMA), trimethylolpropane trimethacrylate (TRIM) and pentaerythritol tetraacrylate (PETA)] were synthesized using organotellurium-mediated living radical polymerization (TERP), which was expected to produce more efficient monolithic columns than conventional free-radical polymerization. The rationale behind selection of porogens, relative concentrations of reagents and polymerization conditions are described. The new monolithic columns were applied to the separation of small molecules (i.e., alkylbenzenes) under isocratic conditions. Chromatographic efficiencies as high as 60,200 plates/m (71,300 plates/m when corrected for extra-column variance) were obtained, showing a general improvement over previous RPLC monoliths.

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Highly cross-linked monolithic networks (i.e., polyethylene glycol diacrylate, PEGDA) synthesized from monomers containing varying ethylene oxide chain lengths were fabricated inside fused silica capillary columns for use in liquid chromatography (LC) of small molecules. Tergitol was used as a surfactant porogen in combination with other typical organic liquid porogens. Column performance was correlated with quantitative descriptors of the physical/chemical properties of the monomers and porogens using a statistical model. Solubility and viscosity values of the components were identified as important predictors of monolith morphology and efficiency. The chromatographic retention mechanism was determined to be principally reversed-phase (RP) with additional hydrogen bonding between the polar groups of the analytes and the ethylene oxide groups embedded in the monolith structure. The fabricated monolithic columns were evaluated under RPLC conditions using phenols, hydroxy benzoic acids, and alkyl parabens as test compounds. Isocratic elution of hydroxy benzoic acids at a linear velocity of 0.04 cm/s using a PEGDA-700 monolith gave chromatographic peaks with little tailing (i.e., tailing factor<1.28). The chromatographic efficiency measured for a non-retained compound (uracil) using this column was 186,000 plates/m when corrected for injector dead volume. High resolution gradient separations of selected pharmaceutical compounds and phenylurea herbicides were achieved in less than 18 min. Optimized monoliths synthesized from all four crosslinking monomers exhibited high permeability and demonstrated little swelling or shrinking in different polarity solvents. Column preparation was highly reproducible, with relative standard deviation (RSD) values less than 2.1%, based on retention times of the phenol standards (3 different columns).

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Monoliths are considered to be a low pressure alternative to particle packed columns for liquid chromatography (LC). However, the chromatographic performance of organic monoliths, in particular, has still not reached the level of particle packed columns. Since chromatographic performance can be attributed to morphological features of the monoliths, in-situ characterization of the monolith structure in three dimensions would provide valuable information that could be used to help improve performance. In this work, serial sectioning and imaging were performed with a dual-beam scanning electron microscope for reconstruction and quantitative characterization of poly(ethylene glycol) diacrylate (PEGDA) monoliths inside a capillary column. Chord lengths, homogeneity factors, porosities and tortuosities were calculated from three-dimensional (3D) reconstructions of two PEGDA monoliths. Chromatographic efficiency was better for the monolith with smaller mean chord length (i.e., 5.23µm), porosity (i.e., 0.49) and tortuosity (i.e., 1.50) compared to values of 5.90µm, 0.59 and 2.34, respectively, for the other monolithic column. Computational prediction of tortuosity (2.32) was found to be in agreement with the experimentally measured value (2.34) for the same column. The monoliths were found to have significant radial heterogeneity since the homogeneity factor decreased from 5.39 to 4.89 (from center to edge) along the column radius.

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Three crosslinking monomers, i.e., 1,6-hexanediol dimethacrylate (HDDMA), cyclohexanediol dimethacrylate (CHDDMA) and 1,4-phenylene diacrylate (PHDA), were used to synthesize highly cross-linked monolithic capillary columns for reversed-phase liquid chromatography (RPLC) of small molecules. Selection of porogen type and concentration was investigated in detail. Isocratic elution of alkylbenzenes at a flow rate of 300nL/min was performed using HDDMA and CHDDMA monolithic columns. Gradient elution of alkylbenzenes using all three monolithic columns showed good separations. Optimized monoliths synthesized from all three crosslinking monomers possessed high permeabilities. Poly(HDDMA) monoliths demonstrated column efficiencies up to 86,000 plates/m. Column preparation of poly(HDDMA) monolithic columns was highly reproducible; the relative standard deviation (RSD) values (n=3) for run-to-run and column-to-column were less than 0.26% and 0.70%, respectively, based on retention times of alkylbenzenes.

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RPLC is the most common mode of LC. It is widely used for separations of both small and large molecules. Monolithic columns, which are currently under intensive study by many groups, have the potential of becoming attractive alternatives to particle-packed columns. They are generally easier and faster to fabricate, and they demonstrate a lower pressure drop, less nonspecific adsorption, and richer chemistry (in the case of organic polymer monoliths) for providing broad selectivity. Silica monoliths, as is also true for columns packed with silica particles, are best applied to small-molecule separations. Organic polymer monoliths, on the other hand, have shown advantages for large-molecule separations. Recently, improvements in organic monoliths have led to efficiencies for small molecules that are approaching and even surpassing 100,000 plates/m. While this performance is still far short of what is currently available using modern small particles and silica monoliths in RPLC, steady progress is being made. This review describes recent developments in the synthesis and performance of organic polymer RPLC monoliths, and identifies areas where additional work is needed to significantly improve their performance for both small- and large-molecule separations.

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This study examined intellectual and memory functioning in a sample of sexually abused children compared to demographically and age-matched controls. The severity of abuse and other pertinent factors were also examined in relation to cognitive performance. Elevated levels of psychopathology were present in the abused children, as well as diminished performance on tasks influenced by attention/concentration. However, after controlling for differences in IQ and socioeconomic status (SES), significant differences in memory function were not found. Results are discussed in the context of stress effects on cognition and the potential resiliency of cognitive function in children undergoing treatment for sexual abuse.

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This study examined the memory performance of children with reading disabilities (RD) using methodology representative of three theoretical perspectives on RD subtypes: the phonological deficit, dual route, and phonological-core variable-difference models. Analyses compared the serial memory, verbal learning, and abstract visual-spatial memory performance of 45 children with RD to that of chronological-age (CA)- and reading-level (RL)-matched controls, using subtype identification methods from each of the theoretical models to classify children with RD. Phonological deficit and dual route comparisons indicated that children with RD, regardless of subtype, performed more poorly than CA- and better than RL-matched participants on all memory tasks. Phonological-core variable-difference methodology yielded three RD subtypes, two of which exhibited distinctive memory deficits relative to both CA and RL control groups. The phonological-core variable-difference model accounted for more variance in memory performance than either of the other two models.

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