Polymeric materials, columns

The polarity values of binary acetonitrile/water and methanol/water mobile phases used in RPLC were measured and compared with methylene selectivity (acH2) for both traditional siliceous bonded phases and for a polystyrene-divinylbenzene resin reversed-phase material [82], The variation in methylene selectivity for both was found to correlate best with percent organic solvent in methanol/water mixtures, whereas the polarity value provided the best correlation in acetonitrile/water mixtures. The polymeric resin column was found to provide higher methylene selectivity than the siliceous-bonded phase at all concentrations of organic solvent. 

Using different polymeric materials in the chromatographic columns and LSC data on retention times (t) of suitably chosen reference solutes, three interfacial parameters (o(p, Ojj, and S), defined below, have been generated for characterizing polymeric membrane materials (53,56)... 

Untreated silica column can be advantageously used for HPLC preseparation of PAHs from triglycerides. The capacity of a silica column to retain fat (for columns of the same particle size) depends on the column size, the mobile phase composition, as well as the type and by-products (free acids and polymerized material) of the fat injected [706,713]. Off-line HPLC-HPLC, employing silica column (250 X 4.6 mm i.d., 5 pm of particle size) for sample preparation before RP-HPLC and spec-trofluorometric detection, was successfully applied for PAH determination in edible oils [659,691] and fish [714]. After PAH elution, the silica column needs to be backflushed with dichloromethane to remove the fat. The entire sample preparation step can be automated by using a backflush valve and a programmable switching valve box [691]. 

To a large bottle are added 116.5 gm (1.0 mole) of 3-chloro-l-hexyne, 20.0 gm (0.20 mole) of cuprous chloride, 16.0 gm (0.30 mole) of ammonium chloride, 10 ml of concentrated hydrochloric acid, 50 ml of water, and 0.6 gm of copper bronze. The bottle is sealed and shaken at room temperature for 14 days. The organic layer is separated, dried over potassium carbonate, and fractionally distilled through a glass-helix-packed column to afford 61.0 gm (52%) of nearly pure l-chloro-l,2-hexadiene, b.p. 54°-57°C (50 mm), p5 1.4567-1.4680, 9.3 gm (8%) of 3-chloro-l-hexyne, and some polymeric material. Shorter periods of reaction give lower yields. The product is purified as described for bromopropadiene. 

Since the dihaloketones may induce the decomposition of the product, it is essential to cool the solution in ice befoie allowing entry of air. Otherwise, the oily cycloadduct becomes brown, and polymeric material has to be removed before crystallization by passage down a 2x5 cm. column of silica gel (impregnated with 12% silver nitrate solution and redried). 

It forms a picrate m 149° (from EtOH-pet ether) from which the free base can be recovered using a basic ion exchange resin and can then be distd through a Todd column using an automatic still head which only collects products boiling below 51°/atm. Polymeric materials if present will boil above this temperature. The hydrochloride has m 85-86°. The pKa in 40% EtOH is 5.33. [Roberts and Chambers JACS 73 5030 1951, Jones JOC 9 484 7944 Emmons J A CS 79 6522 1957. ... 

The crude Bjorkman lignin acidolysis mixture contained both polymeric material and a number of more or less low molecular, chromato-graphically visible products in addition to ketol (XII) and was considered to be a potential source not only of further monomeric but also of dimeric and oligomeric degradation products. The polymeric material was readily removed by filtering the crude mixture of reaction products through a short silica gel column (solvent, dioxane-benzene 1 3). 

If a reaction mixture obtained after 4 hours acidolysis of Bjorkman lignin (spruce), after neutralization and removal of the polymeric material, were filtered through a Sephadex G 25 column, the elution curve (Figure 5) exhibited three peaks (26). The effluent fractions corresponding to peaks A and B were subjected to further fractionation by chromatography on silica gel columns. We found that fraction A contained only monomeric products while fraction B was a mixture of dimeric products (Figures 6 and 7). 

The crystals of the ester E-1 underwent complete reaction within 5 days without any observable melting during conversion. Aside from a small amount of polymeric material (<5%), only a bright yellow substance was formed, which, after column chromatographic separation of the polymeric material, could be isolated in crystalline form in 75% yield. 

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