Sample solvent, effect

The least problematic issues are UV spectral changes as a function of different solvents between the reference and the test sample. Solvent effects on UV spectra in solvents of decreased dielectric constant compared with water parallel solvent effects on apparent pKa. The changes are most marked for acids, for example, leading to a numerical increase of up to two pKa units - an apparent decrease in the acidity of the carboxylic acid. Effects on bases are considerably less. The apparent pKa of a base in a reduced dielectric constant solvent might be up to about half a pKa unit numerically lower (less basic). The UV spectra of neutral compounds... 

Wilson, T. D. Sample solvent effects in an apparent chiral high-performance liquid chromatographic separation on /J-cyclodextrin. Pharm. Sci. Dep., Sterling-Winthrop Res. Inst., Rensselaer, NY, J. Chromatogr. 448(l) 31-39 1988. 

Sample solvent effects on gas chromatographic analyses involve a very different set of considerations. For capillary GC, the effect of the injection solvent has been shown to affect injection precision caused by the expansion volume of the vaporized injection solvent. If the solvent evaporates too fast to a volume larger than the injector volume, then the rapid pressure increase in the injector can cause the sample to leak out through the septum, leading to poor injection precision (11,12). Different solvents have different expansion volumes and expansion rates, therefore proper solvent selection can overcome this problem. Other solutions are smaller injection volume, slower injection speed, or lower injector temperature (11). 

Special solvents that are not components of the mobile phase, but are included in the sample to improve component solubility, will act as though they were solutes themselves. Each will produce a spurious peak somewhere on the chromatogram that must not be misinterpreted as a solute peak. Irrespective of the sample solvent, the solutes of interest must always be sufficiently soluble in the mobile phase to permit effective chromatographic development. 

Results. Various solvent mixtures were tested for extraction efficiency. The test sample was a bone-dry sediment reference material containing 24.6 ppm of Arochlor 1242. This reference material is a real sediment from New Bedford Harbor which was homogenized and carefully assayed for PCB s by the Cincinnati EPA facility. Figure 3 shows recovery of 1242 using (1) hexane alone, (2) hexane and water (1 1), (3) hexane, water, and ethyl ether, (4) ethyl ether and water, (5) ethyl ether, water, and methanol, (6) methanol and hexane (1 1), and (7) water, methanol, and hexane (1 4 5). This last combination appears to give the best recovery. When added in this order to a dry sample, the effect of the water is to wet the sample, thus permitting extraction by methanol. The extracted PCB is partitioned almost exclusively into the hexane from the aqueous methanol. Final recovery is calculated from initial weight and hexane volume. 

For pesticide residue immunoassays, matrices may include surface or groundwater, soil, sediment and plant or animal tissue or fluids. Aqueous samples may not require preparation prior to analysis, other than concentration. For other matrices, extractions or other cleanup steps are needed and these steps require the integration of the extracting solvent with the immunoassay. When solvent extraction is required, solvent effects on the assay are determined during assay optimization. Another option is to extract in the desired solvent, then conduct a solvent exchange into a more miscible solvent. Immunoassays perform best with water-miscible solvents when solvent concentrations are below 20%. Our experience has been that nearly every matrix requires a complete validation. Various soil types and even urine samples from different animals within a species may cause enough variation that validation in only a few samples is not sufficient. 

Many synthetic water-soluble polymers are easily analyzed by GPC. These include polyacrylamide,130 sodium poly(styrenesulfonate),131 and poly (2-vinyl pyridine).132 An important issue in aqueous GPC of synthetic polymers is the effect of solvent conditions on hydrodynamic volume and therefore retention. Ion inclusion and ion exclusion effects may also be important. In one interesting case, samples of polyacrylamide in which the amide side chain was partially hydrolyzed to generate a random copolymer of acrylic acid and acrylamide exhibited pH-dependent GPC fractionation.130 At a pH so low that the side chain would be expected to be protonated, hydrolyzed samples eluted later than untreated samples, perhaps suggesting intramolecular hydrogen bonding. At neutral pH, the hydrolyzed samples eluted earlier than untreated samples, an effect that was ascribed to enlargement... 

Hot splitless WCOT 0.5 ppm (FID) without preconcentration Lower injection temperature than split Trace analysis Handles dirty samples Automation Flash vaporisation Optimisation required (splitless time, oven temperature, solvent) Limited number of solvents ( solvent effect ) Thermal degradation possible Discrimination possible Poor direct quantification Unsuitable for very polar substances... 

Solvent Effects in the Sn Spectra of Poly(TBTM/MMA). Samples of poly(MMA/TBTM) synthesized by the free-radical copolymerization of the appropriate monomers were solutions in benzene with approximately 33% solids (weight to volume). The particular formulation chosen as representative of the class contained a 1 1 ratio of pendant methyl to tri-n-butyltin groups. In preparing the dry polymer, the benzene was removed in vacuo with nominally 5% by weight residual solvent. 

The MD/QM methodology [18] is likely the simplest approach for explicit consideration of quantum effects, and is related to the combination of classical Monte Carlo sampling with quantum mechanics used previously by Coutinho et al. [27] for the treatment of solvent effects in electronic spectra, but with the variation that the MD/QM method applies QM calculations to frames extracted from a classical MD trajectory according to their relative weights. 

Sample Preparation Effects Many methods require the sample to be treated in some way before the analyte can be determined. Examples include drying, grinding or blending of the sample, and extraction or digestion of the sample. Variations in the conditions under which these activities are carried out (e.g. extraction temperature and time, solvent composition) may affect the final result. 

The best way to take advantage of the organic solvent effect without simultaneously diluting the sample is by employing solvent extraction. By this method the element to be analyzed can actually be concentrated and a solution of the element is obtained in essentially pure organic solvent. One of the most commonly used systems involves formation of the metal chelate with ammonium 1-pyrro-lidinecarbodithioate (APDC) and then extracting this into methylisobutyl ketone (MIBK). APDC chelates of many elements form and extract into MIBK from acid solution. 

FIGURE 10 Chromatograms showing the effect of sample solvent and injection volume on peak shape.The peak at 5 min is an impurity in a NCE. Column Supelco Discovery RP amide C16 mobile phase, 2.5% acetonitile in water detection, UV 190 nm injection 10, 20,30,50 and 100 pL sample solvent (A) 2.5% (B) 10% (acetonitrile in water). 

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