Phase condition

Column chiral selector Typical mobile phase conditions Typical analyte features required... 

In most cases, the proteia is immobilized onto y-aminopropyl sUica and covalently attached usiag a cross-linking reagent such as -carbonyl diimidazole. The tertiary stmcture or three dimensional organization of proteias are thought to be important for their activity and chiral recognition. Therefore, mobile phase conditions that cause proteia "deaaturatioa" or loss of tertiary stmcture must be avoided. 

In general, the synthetic polymeric phases seem to have polarities analogous to diol-type phases and a wide range of mobile phase conditions have been used including hexane, various alcohols, acetonitrile, tetrahydrofuran, dichioromethane and their mixtures, as well as aqueous buffers. 

It is seen that as the concentration of C is increased, the tie-lines become shorter because of the increased mutual miscibility of the two phases at the plait point, P, the tie lines vanish. However, P does not necessarily represent the highest possible loading of C which can exist in the system under two-phase conditions. In Figure 2b the plait point Hes on the diagonal because the compositions of the two phases approach each other at P. 

Fluoroaliphatic Thermolytic Routes. The reaction of diduorocarbene (generated from CHCIF2 at 600°C) with cyclopentadiene to give duoroben2ene (70% yield) has been scaled up in a pilot-plant/semiworks faciUty (capacity = several dozen t/yr) (77,78). The same process can now be effected under Hquid-phase conditions in the presence of phase-transfer catalysts (79,80). 

These operations have been gradually replaced by the Mobd-Badger process (28), which employs an acidic ZSM-5 catalyst and produces ethylbenzene using both pure and dilute ethylene sources. In both cases, the alkylation is accomplished under vapor-phase conditions of about 425°C,... 

Control of addition vs substitution by free radicals can be effected by the reaction conditions, ie, radical concentration, temperature, and phase. Using halogens as propylene reactants, high temperatures and the gas phase favor high radical concentrations and substitution reactions cold, Hquid-phase conditions favor addition reactions. 

Droplet Dispersion. The primary feature of the dispersed flow regime is that the spray contains generally spherical droplets. In most practical sprays, the volume fraction of the Hquid droplets in the dispersed region is relatively small compared with the continuous gas phase. Depending on the gas-phase conditions, Hquid droplets can encounter acceleration, deceleration, coUision, coalescence, evaporation, and secondary breakup during thein evolution. Through droplet and gas-phase interaction, turbulence plays a significant role in the redistribution of droplets and spray characteristics. 

High molecular weight primary, secondary, and tertiary amines can be employed as extractants for zirconium and hafnium in hydrochloric acid (49—51). With similar aqueous-phase conditions, the selectivity is in the order tertiary > secondary > primary amines. The addition of small amounts of nitric acid increases the separation of zirconium and hafnium but decreases the zirconium yield. Good extraction of zirconium and hafnium from ca 1 Af sulfuric acid has been effected with tertiary amines (52—54), with separation factors of 10 or more. A system of this type, using trioctylarnine in kerosene as the organic solvent, is used by Nippon Mining of Japan in the production of zirconium (55). 

The first observation of the enantioselective properties of an albumin was made in 1958 (28) when it was discovered that the affinity for L-tryptophan exceeded that of the D-enantiomer by a factor of approximately 100. This led to more studies in 1973 of the separation of DL-tryptophan [54-12-6] C22H22N2O2, on BSA immobilized to Sepharose (29). After extensive investigation of the chromatographic behavior of numerous racemic compounds under different mobile-phase conditions, a BSA-SILICA hplc column (Resolvosil-R-BSA, Macherey-Nagel GmvH, Duren, Germany) was... 

The reactions are highly exothermic. Under Uquid-phase conditions at about 200°C, the overall heat of reaction is —83.7 to —104.6 kJ/mol (—20 to —25 kcal/mol) ethylene oxide reacting (324). The opening of the oxide ring is considered to occur by an ionic mechanism with a nucleophilic attack on one of the epoxide carbon atoms (325). Both acidic and basic catalysts accelerate the reactions, as does elevated temperature. The reaction kinetics and product distribution have been studied by a number of workers (326,327). 

A number of papers have explored methods for the solution of Eqs. (26-29) and (26-31), especially for the two-phase conditions. The reader is referred to the DIERS Project Manual for a more detailed review and list of appropriate references and available computer programs. 

If the motor is switched on, in a single phasing condition, it will not rotate in the absence of a rotating field, similar to a single-phase motor without a start winding. 

Katz et fl/.[l] searched the literature for data that could be used to identify the pertinent dispersion equation for a packed column in liquid chromatography. As a result of the search, no data was found that had been measured with the necessary accuracy and precision and under the sufficiently diverse solute/mobile phase conditions required to meet the second criteria given above. It became obvious that a... 

Select suitable mobile phase condition. Choose a mobile phase that will solubilize the sample and will be compatible with the column packing material. 

Select mobile phases for HPSEC based on their ability to dissolve the sample and their compatibility with the column. Zorbax PSM columns are compatible with a wide variety of organic and aqueous mobile phases (Table 3.4), but analysts should avoid aqueous mobile phases with a pH greater than 8.5. As mentioned earlier, select mobile phases that minimize adsorption between samples and silica-based packings. Sample elution from the column after the permeation volume indicates that adsorption has occurred. If adsorption is observed or suspected, select a mobile phase that will be more strongly adsorbed onto the silica surface than the sample. For example, N,N-dimethyl-formamide (DMF) is often used for polyurethanes and polyacrylonitrile because it eliminates adsorption and dissolves the polymers. When aqueous mobile phases are required, highly polar macromolecules such as Carbowax can be used to coat the silica surface and eliminate adsorption. Table 3.5 provides a list of recommended mobile-phase conditions for some common polymers. 

The hydrophilic surface characteristics and the chemical nature of the polymer backbone in Toyopearl HW resins are the same as for packings in TSK-GEL PW HPLC columns. Consequently, Toyopearl HW packings are ideal scaleup resins for analytical separation methods developed with TSK-GEL HPLC columns. Eigure 4.44 shows a protein mixture first analyzed on TSK-GEL G3000 SWxl and TSK-GEL G3000 PWxl columns, then purified with the same mobile-phase conditions in a preparative Toyopearl HW-55 column. The elution profile and resolution remained similar from the analytical separation on the TSK-GEL G3000 PWxl column to the process-scale Toyopearl column. Scaleup from TSK-GEL PW columns can be direct and more predictable with Toyopearl HW resins. 

Electronic structure methods are aimed at solving the Schrodinger equation for a single or a few molecules, infinitely removed from all other molecules. Physically this corresponds to the situation occurring in the gas phase under low pressure (vacuum). Experimentally, however, the majority of chemical reactions are carried out in solution. Biologically relevant processes also occur in solution, aqueous systems with rather specific pH and ionic conditions. Most reactions are both qualitatively and quantitatively different under gas and solution phase conditions, especially those involving ions or polar species. Molecular properties are also sensitive to the environment. 

In addition to two-phase conditions, phase transfer catalysts have been used to improve the Skraup/Doebner-von Miller reaction.Condensation of 32 with 5 in a two-phase system of toluene/con HCI provides 33 in 47% yield. Addition of 5 mol% tetra- -butyl ammonium chloride increased the yield to 57%. 

Fig. 3-1. Separation of racemic 3,5-dinitrobenzamido leucine Al.A -diallylamide on silica and polymer-based chiral stationary phases. Conditions column size 150 x 4.6 mm i.d. mobile phase 20 % hexane in dichloromethane flowrate 1 mL min injection 7 pg. Peaks shown are l,3,5-tri-rert.-butylbenzene (1), R-enantiomer (2) 5-enantiomer (2 ). (Reprinted with permission from ref. [8]. Copyright 1997 American Chemical Society.)...

The brush-type (Pirkle-type) CSPs have been used predominantly under normal phase conditions in LC. The chiral selector typically incorporates tt-acidic and/or n-basic functionality, and the chiral interactions between the analyte and the CSP include dipole-dipole interactions, n-n interactions, hydrogen bonding, and steric hindrance. The concept of reciprocity has been used to facilitate the rational design of chiral selectors having the desired selectivity [45]. 

Column selection remains the most important factor in successful enantiomeric separations. The CSPs most likely to be effective in SFC are those that have been employed under normal phase conditions in LC. In fact, the tremendous body of knowledge that has been accumulated for LC can also guide column selection in SFC [66]. The likelihood of success with a particular CSP can generally be gauged after one or two injections [67]. If no evidence of separation is observed, another CSP should be investigated. 

Both reactions were carried out under two-phase conditions with the help of an additional organic solvent (such as iPrOH). The catalyst could be reused with the same activity and enantioselectivity after decantation of the hydrogenation products. A more recent example, again by de Souza and Dupont, has been reported. They made a detailed study of the asymmetric hydrogenation of a-acetamidocin-namic acid and the kinetic resolution of methyl ( )-3-hydroxy-2-methylenebu-tanoate with chiral Rh(I) and Ru(II) complexes in [BMIM][BF4] and [BMIM][PFg] [55]. The authors described the remarkable effects of the molecular hydrogen concentration in the ionic catalyst layer on the conversion and enantioselectivity of these reactions. The solubility of hydrogen in [BMIM][BF4] was found to be almost four times higher than in [BMIM][PFg]. 

When water comes in contact with the chloro-fluoro-refrigerants, an acid condition is established. This moisture may be in the form of water vapor coming in with air and is more likely if the suction side is lower than atmospheric pressure. These systems must be checked for leaks and moisture content. The descending order of reactivity with water is refrigerants 11, 12, 114, 22, and 113. Water vapor does not affect ammonia, except to modify the pressure-temperature relationship. When this becomes noticeable, the charge must be dried. Water must be purged from hydrocarbon systems, because emulsions or two-phase conditions may develop. 

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