Capillary Pretreatment

A separation with sharp peaks for sample ions and reproducible migration times requires a clean capillary surface. This is usually accomplished by frequent rinsing of the capillary with dilute aqueous sodium hydroxide. After a water rinse, the capillary is filled with the background electrolyte (BGE) solution. The BGE contains a pH buffer and a sufficient concentration of an electrolyte (frequently 20-50 mM) to maintain a steady current. 

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Capillary conditions these are affected by the capillary pretreatment reagents (e.g., NaOH) or dynamic capillary coating systems to achieve better reproducibility. 

FIG. 13 Kinetics of evaporation L t) of water from native quartz capillary (curve 1) and from the capillary pretreated with CA solution in ethanol (curve 2) at pjp = 0.48, r = 7.6 pm. 

Figure 11.13 (a-c) Immunoaffinity exti action-SPE-GC-FID ti aces of (a) HPLC-grade water (b) urine (c) urine spiked with /3-19-noitestosti one (0.5 p.g/1) or norethindrone and norgestrel (both 4 p.g/1) (d) SPE-GC-FID ti ace of urine. Reprinted from Analytical Chemistry, 63, A. Faijam et al., Direct inti oduction of large-volume urine samples into an on-line immunoaffinity sample pretreatment-capillary gas cliromatography system, pp. 2481-2487,1991, with permission from the American Chemical Society. 

A multidimensional system using capillary SEC-GC-MS was used for the rapid identification of various polymer additives, including antioxidants, plasticizers, lubricants, flame retardants, waxes and UV stabilizers (12). This technique could be used for additives having broad functionalities and wide volatility ranges. The determination of the additives in polymers was carried out without performing any extensive manual sample pretreatment. In the first step, microcolumn SEC excludes the polymer matrix from the smaller-molecular-size additives. There is a minimal introduction of the polymer into the capillary GC column. Optimization of the pore sizes of the SEC packings was used to enhance the resolution between the polymer and its additives, and smaller pore sizes could be used to exclude more of the polymer... 

Sun, X. et al., Capillary electrophoresis with amperometric detection of curcumin in Chinese herbal medicine pretreated by solid-phase extraction, J. Chromatogr. A, 962, 117, 2002. 

Four mmoles of malononitrile and benzaldehyde were introduced in a batch stirred tank reactor at 323 K with toluene as solvent (30 ml). Then 0.05 g of aluminophosphate oxynitride was added. Samples were analysed by gas chromatography (Intersmat Delsi DI200) using a capillary column (CPSilSCB-25 m). Care was taken to avoid mass or heat transfer limitations. Before the reaction no specific catalyst pretreatment was done. 

The catalytic ethylene oligomerization was performed in a 0.3 L well-mixed three-phase reactor operating in semi-batch mode, at constant temperature (70 or 150 °C) and pressure (4 MPa of ethylene) in 68 g of n-heptane (solvent). Prior to each experiment, the catalyst was successively pretreated, firstly in a tubular electrical furnace (550 °C, 8 h) and then in the oligomerization autoclave (200 °C, 3 h), under nitrogen flow at atmospheric pressure. After 30 min of reaction, the autoclave was cooled at -20 °C and the products were collected, weighted and analyzed by GC (FID, DB-1 60 m capillary column). 

A sensitive determination of organotin compounds in sediments is based on separation of the chlorides R SnCl4- , n = 1-3, R = Me, n-Bu, Ph, by GC-FPD or GC-ECD using a DB-608 open tubular column with HC1 doping of the carrier gas LOD 30 ng Sn/g of sediment77. A modification of this method uses GC-FPD with DB-1 capillary column and a 611.5 nm filter. The column requires special pretreatment with an HBr/EtOAc solution78. 

The efficacy of CE separation depends considerably on the type of capillary. Fused-silica capillaries without pretreatment are used most frequently. Its outside is coated with a polymer layer to make it flexible and to lessen the occurrence of breakage. The polymer coating has to be dissolved with acid or burned away at the detection point. Capillaries with an optically transparent outer coating have also found application in CE. The objectives of the development of chemically modified capillary walls were the elimination of electro-osmotic flow and the prevention of adsorption on the inner wall of the capillary. Another method to prevent the adsorption of cationic analyses and proteins is the use of mobile phase additives. The modification of the pH of the buffer, the addition of salts, amines and polymers have all been successfully employed for the improvement of separation. 

The migration order of wine anthocyanins in CE has been studied in detail and the results have been compared with those obtained by RP-HPLC-MS. Wines were filtered and used for the analyses without any other pretreatment. Wine samples of 10 ml were freeze-dried, redissolved in methanol and applied for semi-preparative fractionation. CZE measurements were carried out in a fused-silica capillary (46 cm effective length, 75 /an i.d.). The capillary was conditioned with 0.1 M NaOH (2 min), water (2 min) and running buffer (5 min). The buffer consisted of 50 mM sodium teraborate (pH = 8.4) containing 15 per cent (v/v)... 

An electrophoretic method was developed for the simultaneous determination of artificial sweeteners, preservatives and colours in soft drinks. The samples were degassed by sonication, filtered and used for analysis without any other pretreatment. Measurements were realized in uncoated fused-silica capillaries, the internal diameter being 50 ptm. Capillary lengths were 48.5 cm (40 cm to the detector) and 65.4 cm (56 cm to the detector). Capillaries were conditioned by washing them with (1 M sodium hydroxide (10 min), followed by 0.1 M sodium hydroxide (5 min) and water (5 min). Samples were injected hydrodinamically (250 mbar) at the anodic end. Analyses were performed at a voltage of 20 kV and the capillary temperature was 25°C. Analytes having ionizable substructure... 

Altria, K. D., and Rogan, M. M. (1990). Reductions in sample pretreatment requirements by using high-performance capillary electrokinetic separation methods. J. Pharm. Biomed. Anal. 8, 1005-1008. 

The majority of commercial developments which relate to the automation of GC and HPLC pay little attention to sample preparation. There are few examples where pretreatment is not required. A fully automated system was developed by Stockwell and Sawyer [23] for the determination of the ethanol content of tinctures and essences to estimate the tax payable on them. An instrument was designed and patented which coupled the sample pre-treatment modules, based on conventional AutoAnalyzer modules, to a GC incorporating data-processing facihties. A unique sample-injection interface is used to transfer samples from the manifold onto the GC column. The pretreated samples are directed to the interface vessel hy a simple hi directional valve. An ahquot (of the order of 1 ml) can then he injected on to the GC column through the capillary tube using a time-over pressure system. 

Wang F, Ji Z, Wang D. 1991. A rapid pretreatment procedure for determining trace organochlorine compounds in biological samples by capillary gas chromatography. Microchemical Journal 44 67-71. 

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