Deactivation of silica

Deactivation of silica gel and preparation of the column is carried out as in Note 6, except that the checkers consider 20 g. of silica gel per gram of crude product to be adequate in this case. Running through a gradient of petroleum ether containing increasing amounts of ether, the submitters found that the product was eluted with 15% vjv ether, and the checkers found that 25% vjv ether was required. 

Table 7.89 lists the main characteristics of MDHPLC (see also Table 7.86). In MDHPLC the mobile-phase polarity can be adjusted in order to obtain adequate resolution, and a wide range of selectivity differences can be employed when using the various available separation modes [906]. Some LC modes have incompatible mobile phases, e.g. normal-phase and ion-exchange separations. Potential problems arise with liquid-phase immiscibility precipitation of buffer salts and incompatibilities between the mobile phase from one column and the stationary phase of another (e.g. swelling of some polymeric stationary-phase supports by changes in solvents or deactivation of silica by small amounts of water).

Kiss, G., KJiewer, C. E., DeMartin, G. J., Culross, C. C., and Baumgartner, J. E. 2003. Hydrothermal deactivation of silica-supported cobalt catalysts in Fischer-Tropsch synthesis. J. Catal. 217 127-40. 

Several groups have reported deactivation of silica-supported cobalt catalysts. Holmen and coworkers19 30 have reported increased deactivation due to added (external) water in the feed to silica-supported Co catalysts. Kogelbauer et al 1 reported the formation of silicates. Catalysts recovered from FTS as well as catalysts deactivated by steam-treatment both showed fractions of non-reducible cobalt in TPR. The presence of metallic cobalt was a prerequisite for the silicate formation. 

One of the first steps in modifying the performance of capillary electrophoresis was the deactivation of silica groups of the capillary column by physically coating the capillary wall with methylcellulose (58,59), as well as via silane derivatization (10,44,60). Presently, many other changes have been carried out either to the capillary surface or addition of chemical agents to the separation buffer (see Table II), including manipulation of... 

Acid catalysts such as zeolites can be readily poisoned by basic organic compounds. One of the earlier studies of the deactivation of silica-alumina cracking catalysts by organic nitrogen compounds such as quinoline, quinaldine, pyrrole, piperidine, decylamine and aniline was done by Mills et al (6). The results of their partial poisoning studies showed an exponential dependence of the catalyst activity for cumene cracking reaction or... 

Deactivation of silica surfaces by grafting of alkyl chains [esterification with short-chain (Ci) or long-chain (Ci6) alcohols] was reported (24) to be associated with strong decreases in 7sd as well as 7sp, which for Ci6-modified samples are very close to those exhibited by polyethylene (known to be a... 

M. Cabucicchio, F. Forzatti, F. Trifiro, E. Tronconi, and P. Villa, "Deactivation of Silica Supported Fe203-Mo03 Catalyst for the Oxidation of Methanol", in Catalyst Deactivation, eds. Delmon Froment, Elsevier, Amsterdam, 1980, pp. 103-113. 

It has long been recognized that water deactivation of silica, alumina. 

The absolute Rp value and its reproducibility on inorganic oxide layers depends on the layer activity. This is controlled by the adsorption of reagents, most notably water, through the gas phase [100]. Physically adsorbed water is removed from silica gel layers by heating at about 120°C for 30 minutes. Afterwards the plates are stored over a drying agent in a grease-free desiccator. Heat activation is not usually required for chemically bonded layers. Deactivation of silica gel layers by exposure to the atmosphere is extremely rapid. In modern environment-controlled laboratories, layers achieve a consistent level of activity almost instantaneously, that should provide sufficient reproducibility for most separations. Indeed, brief exposure of activated layers to the laboratory atmosphere may render the activation process a waste of effort. 

Purified by chromatography on a column of deactivated alumina or magnesium oxide, or on a thin layer of silica gel G (Merck), using dichloromcthane/dicthyl ether (9 1) to develop the chromatogram. Stored in the dark and in an inert atmosphere at -20 . 

Purified by chromatography on partially deactivated alumina or magnesia, or by using a thin layer of silica gel G with 4 1 cyclohexane/diethyl ether as the developing solvent. Stored in the dark at -20°. 

A solution of diazomethane in 2.4 liters ether, prepared from 177 g (1.71 moles) of A-nitrosomethylurea and 530 ml of 40% aqueous potassium hydroxide, is added to 26.4 g (0.81 moles) 17 -acetoxyandrosta-1,4,6-triene-3-one in 250 ml ether. After 6 days at room temperature the ether is removed by distillation at reduced pressure and the residue is chromatographed on 1.5 kg of silica gel (deactivated with water 10% v/w). The product is eluted with methylene dichloride and recrystallized from diisopropyl ether-methylene dichloride to give 11 g (37 %) 17 -acetoxyandrosta-4,6-dien-3-one-[2a,la-c]-A -pyrazoline mp 161° (dec.) —91° (CHCI3) ... 

Figure 12.7 Cliromatograms of a polycarbonate sample (a) microcolumn SEC ti ace (b) capillary GC ti ace of inti oduced fractions. SEC conditions fused-silica (30 cm X 250 mm i.d.) packed with PL-GEL (50 A pore size, 5 mm particle diameter) eluent, THE at aElow rate of 2.0ml/min injection size, 200 NL UV detection at 254 nm x represents the polymer additive fraction ti ansfeired to EC system (ca. 6 p-L). GC conditions DB-1 column (15m X 0.25 mm i.d., 0.25 pm film thickness) deactivated fused-silica uncoated inlet (5 m X 0.32 mm i.d.) temperature program, 100 °C for 8 min, rising to 350 °C at a rate of 12°C/min flame ionization detection. Peak identification is as follows 1, 2,4-rert-butylphenol 2, nonylphenol isomers 3, di(4-tert-butylphenyl) carbonate 4, Tinuvin 329 5, solvent impurity 6, Ii gaphos 168 (oxidized). Reprinted with permission from Ref. (14).

A solution of 4.5 g (19.9 mmol) 4-(fm-butyldimethylsilyloxy)-2-cyclohexenone and 452 mg (1 mmol) of mercury(II) iodide is stirred at r.t. for 15 min and then cooled to — 78 °C. 5.03 g (24.8 mmol) of 1-ethoxy-1-(tm-bulyl(iimethylsilyloxy)ethene are added dropwise during 15 min. The mixture is stirred at — 78 °C for 2 h, quenched with 302 mg (3 mmol) of triethylamine and allowed to warm to r.t. The mixture is filtered through a short (3 cm) column of silica gel (deactivated with a 5% triethylamine solution in hexane/ethyl acetate, 10 1) eluting with hexane/ethyl acetate (10 1) and concentrated in vacuo. Purification of the crude material by flash chromatography (silica gel, hcxanc/cthyl acetate 30 1) gave the adduct as a colorless oil yield 7.98 g (18.7 mmol, 94%) d.r. (cisjtrans) 95.2 4.8. 

Capillary column A narrow bore tube (0.25-1 mm ID) typically 30-100 m long (usually of deactivated fused silica), whose walls are coated with a liquid stationary phase to produce high-efficiency separations (N > 100,000). 

Thus, the column should completely resolve about 14 equally spaced peaks. It is seen from figure 1 that a peak capacity of 14 is not realized although most of the components are separated. This means that the column may not have been packed particularly well and/or the flow rate used was significantly above the optimum velocity that would provide the maximum efficiency. The mobile phase that was used was tetrahydrofuran which was sufficiently polar to deactivate the silica gel with a layer (or perhaps bilayer) of adsorbed solvent molecules yet was sufficiently dispersive to provide adequate sample... 

It is seen that to identify the impurities, the column appeared to be significantly overloaded. Nevertheless, the impurities were well separated from the main component and the presence of a substance was demonstrated in the generic formulation that was not present in the Darvocet . The mobile phase was 98.5% dichloromethane with 1.5% v/v of methanol containing 3.3% ammonium hydroxide. The ammoniacal methanol deactivated the silica gel but the interaction of the solutes with the stationary phase would still be polar in nature. In contrast solute interactions with the methylene dichloride would be exclusively dispersive. 

It is well known that flnorescence from an RP-18 phase is much brighter than from a silica gel plate, because the coating of RP-18 material blocks nomadiative deactivation of the activated sample molecules. By spraying a TLC plate with a viscous liquid, e g., paraffin oil dissolved in hexane (20 to 67%), the fluorescence of a sample can be tremendously enhanced. The mechanism behind fluorescence enhancement is to keep molecules at a distance either from the stationary layer or from other sample molecules [14]. Therefore, not only paraffin oil, but a number of different molecules show this enhancement effect. 

Preparation of column. Pack the chromatographic tube in the following order a quartz-wool plug, 1.0 g of silica gel (deactivated with 1.5% water), then a 5-10-mm layer of sodium sulfate. Finally, insert a small amount of quartz-wool on top of the column packing. Before use, rinse the column with 5 mL of n-hexane and discard the eluate. 

Silica gel column cleanup. Prepare a silica gel column by placing a glass-wool plug in the bottom of a glass chromatography column. Slurry 15 g of silica gel (deactivated with 10% water) with hexane, and transfer the slurry to the column. Rinse the walls of the column with hexane and add 2 g of sodium sulfate to the top of the silica gel column. Drain the hexane to the top of the sodium sulfate layer. 

Adsorption or catalytic decomposition of labile substances by the syringe needle can be a problem for some compounds using hot vaporizing injectors [25]. For open tubular columns deactivated fused silica syringe needles and cold on-column Injection techniques are used to minimize this problem. Alternatively, syringes fitted with a needle shroud for cold-needle injection can be used [26]. 

Figure 9.9 Schesatic diagrans of flow-through cell. A, and solvent elimination interfar B, for SFC/FTIR. For A (1) polished stainless steel lig..v.pipe (2) zinc selenide window (3) PTFE spacer (4) viton rubber o-ring (5) graphitized Vespel nicroferrule (6) deactivated fused-silica capillary tubing (7) bolt with Allen nut (8) stainless steel end-fitting and (9) stainless steel body of flow cell.

Figure 2.6 Reagents used for the deactivation of silanol groups on glass surfaces. A - disilazanes, B > cyclic siloxanes, and C -silicon hydride polysiloxanes in which R is usually methyl, phenyl, 3,3,3-trifluoropropyl, 3-cyanopropyl, or some combination of these groups. The lover portion of the figure provides a view of the surface of fused silica with adsorbed water (D), fused silica surface after deactivation with a trimethylsilylating reagent (E), and fused silica surface after treatment with a silicon hydride polysiloxane (F).

Zirconium, titanium, and hafnium hydrides can activate the C-H bonds of several alkanes at low temperatures (even at room temperature) because they are very electrophilic and reactive. Moreover, the surface complex is immobilized by the strong metal-silica bonds, and this immobilization can prevent the coupling reactions leading to the deactivation of the complex. 

For the Ti(OiPr)4/silica system, the advantage of MCM-41 (a mesoporous silica) over an amorphous silica is not evident either in terms of activity or selectivity for the epoxidation of cyclohexene with H202 in tert-butyl-alcohol.148 Nevertheless, deactivation of the catalysts seems slower, although the selectivity of the recovered catalysts is also lower (allylic oxidation epoxidation = 1 1). Treatment of these solids with tartaric acid improves the properties of the Ti/silica system, but not of the Ti/MCM-41 system, although NMR,149 EXAFS,150 and IR151 data suggest that the same titanium species are present on both supports. 

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