Retention definition

Stereoselectivity. See Asymmetric induction Axial/equatorial-, Cis/trans-, Enantio-, Endo/exo- or Erythro/threo-Selectivity Inversion Retention definition (e.e.), 107 footnote Steric hindrance, overcoming of in acylations, 145 in aldol type reactions, 55-56 in corrin synthesis, 261-262 in Diels-Alder cyclizations, 86 in Michael type additions, 90 in oiefinations Barton olefination, 34-35 McMurry olefination, 41 Peterson olefination, 33 in syntheses of ce-hydrdoxy ketones, 52 Steric strain, due to bridges (Bredt s rule) effect on enolization, 276, 277, 296, 299 effect on f3-lactam stability, 311-315 —, due to crowding, release of in chlorophyll synthesis, 258-259 in metc-cyclophane rearrangement, 38, 338 in dodecahedrane synthesis, 336-337 in prismane synthesis, 330 in tetrahedrane synthesis, 330 —, due to small angles, release of, 79-80, 330-333, 337... 

Equation fl7-421 or f 17-431 are the RT equations for UF. They are particularly sinple because the inherent rejection R° is based on experimental data. Note that the retention definition for UF is microscopic, which is different than the macroscopic definition used for RO (Eq. ri7-24all. The RT equations for UF depend only on the inherent solute rejection and M. For a perfectly mixed membrane module we assume tiiat Xj. = x. Then either Eq. tl7-421 or 117-431 written in terms of can be solved... 

Fn some cases, r-allylpalladium complex formation by retention syn attack) has been observed. The reaction of the cyclic allyiic chloride 33 with Pd(0) affords the 7r-allylpalladium chlorides 34 and 35 by retention or inversion depending on the solvents and Pd species. For example, retention is observed in benzene, THF, or dichloromethane with Pd2(dba)3. However, the complex formation proceeds by inversion in these solvents with Pd(Ph3P)4, whereas in MeCN and DMSO it is always inversion[33]. The syn attack in this case may be due to coordination of Pd to chlorine in 33, because Pd is halophilic. The definite syn attack in complex formation has been observed using stereoche-mically biased substrates. The reaction of the cxoallylic diphenylphosphino-acetate 36 with phenylzinc proceeds smoothly to give 37. The reaction can be explained by complex formation by a syn mechanism[31]. However, these syn attacks are exceptional, and normally anti attack dominates. 

The definition of polymer thermal stabiUty is not simple owing to the number of measurement techniques, desired properties, and factors that affect each (time, heating rate, atmosphere, etc). The easiest evaluation of thermal stabiUty is by the temperature at which a certain weight loss occurs as observed by thermogravimetric analysis (tga). Early work assigned a 7% loss as the point of stabiUty more recentiy a 10% value or the extrapolated break in the tga curve has been used. A more reaUstic view is to compare weight loss vs time at constant temperature, and better yet is to evaluate property retention time at temperature one set of criteria has been 177°C for 30,000 h, or 240°C for 1000 h, or 538°C for 1 h, or 816°C for 5 min (1). 

When a flocculated feed is added to a filter tank, there is a definite time lag before this material reaches the surface of the filter medium. Since this lag time is not known at the time of testing, a lag time of 8 to 10 minutes should be allowed before starting the first leaf test on a flocculated shiny. Two, or perhaps three, tests can be run before the elapsed time exceeds the probable retention time in the full-scale filter tank. With knowledge of the elapsed time after flocculation and data relating to the rate of degradation, the rates obtained on the leaf test runs can be adjusted to some constant lag time consistent with the anticipated full-sc e design. 

Depth tends to be determined from the retention time and the surface overflow rate. As surface overflow rates were reduced, the depth of sedimentation tanks was reduced to keep retention time from being excessive. It was recognized that depth was a valid design parameter and was more critical in some systems than retention time. As mixed-liquor suspended-solids (MESS) concentrations increase, the depth should also be increased. Minimum sedimentation-tank depths for variable operations should be 3.0 m (10 ft) with depths to 4.5 m (15 ft) if 3000 mg/L MESS concentrations are to be maintained under variable hydraulic conditions. With MESS concentrations above 4000 mg/L, the depth of the sedimentation tank should be increased to 6.0 m (20 ft). The key is to keep a definite freeboard over the settled-sludge blanket so that variable hydraulic flows do not lift the solids over the effluent weir. 

The retentivity relative to solid particles (e.g., spherical particles of polystyrene of definite size) is found from experiments determining the amount of these particles in the suspension to be filtered before and after the filter media. The retentivity K is determined as follows where g, g" =amounts of solid particles in liquid sample before and after the medium, respectively. 

It was anticipated all along that the vinylsilane residue could serve as a vinyl iodide surrogate. After protection of the C-14 secondary hydroxyl in 180 in the form of a triisopropylsilyl ether, the vinyltrimethylsilyl function can indeed be converted to the requisite vinyl iodide with AModosuccinimide (NIS) (see 180—>181, Scheme 43). Vinyl iodide 181 is produced stereospecifically with retention of the A17,18 double bond geometry. This transformation is stereospecific since the stereochemistry of the starting vinylsilane and the vinyl iodide product bear a definite relationship to each other.67b 75... 

The kinetics and stereochemical data definitely point to a transient aziridinone of inverted configuration 2 among the further potential intermediates (Fig. 5). Reactions of aziridinone 2 with a nucleophile would allow the crucial bond of the product Ifl to form through a second inversion (overall retention). This pathway... 

A general approach to the problem of identification, should more definitive detectors not be available, is to change the chromatographic system , which in the case of HPLC is usually the mobile phase, and redetermine the retention parameter. The change obtained is often more characteristic of a single analyte than is the capacity factor with either of the mobile phases. 

A more definitive identification may be obtained by combining retention characteristics with more specific information from an appropriate detector. Arguably, the most information-rich HPLC detectors for the general identification problem are the diode-array UV detector, which allows a complete UV spectrum of an analyte to be obtained as it elutes from a column, and the mass spectrometer. The UV spectrum often allows the class of componnd to be determined but the... 

Chlorambucil - there is no problem with the quantitation ion (at m/z 254), although the second ion proves to be a little difficult. While the ion at m/z 303 is the obvious choice, this is not very intense and therefore for samples containing small amounts of analyte the precision of measurement of this ion will be reduced and it may not be detectable at all levels at which the quantitation ion is observed. We could possibly consider the (M- -2) ion, as the combination o/m/z 254 (high mass, and therefore reasonable specificity), the presence of one chlorine, and the chromatographic retention time could be considered sufficient for definitive identification in those cases in which the intensity o/m/z 303 is insufficient. 

The need for a more definitive identification of HPLC eluates than that provided by retention times alone has been discussed previously, as have the incompatibilities between the operating characteristics of liquid chromatography and mass spectrometry. The combination of the two techniques was originally achieved by the physical isolation of fractions as they eluted from an HPLC column, followed by the removal of the mobile phase, usually by evaporation, and transfer of the analyte(s) into the mass spectrometer by using an appropriate probe. 

It is important to note that the matrix effects, interferences, and variability in method efficiency are to be factored in when determining the MDL. If this was not done then only the background noise (see Figure 2, peak 13) would be considered in the definition of the MDL. In real-life samples there is a good possibility that matrix component peaks would either co-elute or elute at retention times close to... 

By definition, the e]q>erlmentally determined average mobile phase velocity Is equal to the ratio of the column length to the retention time of an unretalned solute. The value obtained will depend on the ability of the unretalned solute to probe the pore volume. In liquid chromatography, a value for the Interstitial velocity can be obtained by using an unretalned solute that Is excluded from the pore volume for the measurement (section 4.4.4). The Interstitial velocity Is probably more fundamentally significant than the chromatographic velocity in liquid chromatography (39). 

It is critically important to recognize that the treatments of hyperkalemia discussed thus far are transient, temporizing measures. They are intended to provide time to institute definitive therapy aimed at removing excess potassium from the body. Agents that increase potassium excretion from the body include sodium polystyrene sulfonate, loop diuretics, and hemodialysis or hemofiltration (used only in patients with renal failure). Sodium polystyrene sulfonate (Kayexalate , various manufacturers) can be given orally, via NG tube, or as a rectal retention enema and is dosed at 15 to 60 grams in four divided doses per day. 

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