Resins, solution purification

Supported reagent philosophy is the blueprint of SPS. In this approach the substrate is kept in solution while reagents are bound to resins. Hence, purification also consists of a simple filtration but the reaction product is recovered in the filtrate. As a consequence, it can be analysed by classical means and reactions optimized very easily. More and more supported reagents and catalysts are now commercially available. 

The synthesis of a heptaglucoside has been efficiendy accomplished on a PEG-support as depicted in Scheme 3.8.1. After each coupling step, the product was precipitated and purified by washing of the residue. Subsequent deprotection, cleavage from the resin and purification yielded the final oligosaccharide in 18% yield. The product had the same biological activity as a reference sample prepared previously by standard solution methodology. ... 

From a manufacturing standpoint, the interfacial process is capital-intensive to purify the resin solution, isolate and dry the resin, and recycle solvents and brine. With melt transesterification, because it is a solventless process, the only recycle streams that must be dealt with are those related to the recovery of phenol for reuse in the production of DPC. Hence, there is no need to invest in solvent recovery infrastructure with the melt process, and polymer purification units and dryers can likewise be avoided. However, these investments are somewhat diminished by the investment required for the preparation and purification of DPC. 

The hydrophihc calystegines are extracted with water or methanol-water solutions. After centrifugation, the volume of the supernatant is reduced, treated with skin powder, filtered, and then applied to columns of strongly acidic cation exchange resin for purification. The nonbinding compounds are removed with water and alkaloids are eluted with 3.5% aqueous NH3. After drying, the alkaloid fraction has to be silylated for further GC-MS analysis [20]. 

After preparation, colloidal suspensions usually need to undergo purification procedures before detailed studies can be carried out. A common technique for charged particles (typically in aqueous suspension) is dialysis, to deal witli ionic impurities and small solutes. More extensive deionization can be achieved using ion exchange resins. 

The major disadvantage of solid-phase peptide synthesis is the fact that ail the by-products attached to the resin can only be removed at the final stages of synthesis. Another problem is the relatively low local concentration of peptide which can be obtained on the polymer, and this limits the turnover of all other educts. Preparation of large quantities (> 1 g) is therefore difficult. Thirdly, the racemization-safe methods for acid activation, e.g. with azides, are too mild (= slow) for solid-phase synthesis. For these reasons the convenient Menifield procedures are quite generally used for syntheses of small peptides, whereas for larger polypeptides many research groups adhere to classic solution methods and purification after each condensation step (F.M. Finn, 1976). 

The ratio of reactants had to be controlled very closely to suppress these impurities. Recovery of the acrylamide product from the acid process was the most expensive and difficult part of the process. Large scale production depended on two different methods. If soHd crystalline monomer was desired, the acrylamide sulfate was neutralized with ammonia to yield ammonium sulfate. The acrylamide crystallized on cooling, leaving ammonium sulfate, which had to be disposed of in some way. The second method of purification involved ion exclusion (68), which utilized a sulfonic acid ion-exchange resin and produced a dilute solution of acrylamide in water. A dilute sulfuric acid waste stream was again produced, and, in either case, the waste stream represented a... 

Molecular Weight. Measurement of intrinsic viscosity in water is the most commonly used method to determine the molecular weight of poly(ethylene oxide) resins. However, there are several problems associated with these measurements (86,87). The dissolved polymer is susceptible to oxidative and shear degradation, which is accelerated by filtration or dialysis. If the solution is purified by centrifiigation, precipitation of the highest molecular weight polymers can occur and the presence of residual catalyst by-products, which remain as dispersed, insoluble soHds, further compHcates purification. 

Recovery and Purification. The dalbaheptides are present in both the fermentation broth and the mycelial mass, from which they can be extracted with acetone or methanol, or by raising the pH of the harvested material, eg, to a pH of 10.5—11 for A47934 (16) (44) and A41030 (41) and actaplanin (Table 2) (28). A detailed review on the isolation of dalbaheptides has been written (14). Recovery from aqueous solution is made by ion pair (avoparcin) or butanol (teicoplanin) extraction. The described isolation schemes use ion-exchange matrices such as Dowex and Amberlite IR, acidic alumina, cross-linked polymeric adsorbents such as Diaion HP and Amberlite XAD, cation-exchange dextran gel (Sephadex), and polyamides in various sequences. Reverse-phase hplc, ion-exchange, or affinity resins may be used for further purification (14,89). 

The residue is leached to give cesium sulfate solution, which can be converted to cesium chloride by ion exchange on Dowex 50 resin and elution with 10% HCl, treatment using ammonia or lime, to precipitate the alurninum, or by solvent extraction, followed by purification at neutral pH using hydrogen peroxide or ammonia. 

The caprolactam obtained must meet die specifications of permanganate number, volatile bases, hazen color, UV transmittance, solidification point, and turbidity in order to be used for repolymerization alone or in combination witii virgin CL.5 Reported CL purification methods include recrystallization, solvent extraction, and fractional distillation. One solvent extraction technique involves membrane solvent extraction. Ion exchange resins have been shown to be effective in the purification of aqueous caprolactam solutions. In one such process,... 

Analyses for the Saxitoxins. Early methods for analysis of the saxitoxins evolved from those used for toxin isolation and purification. The principal landmarks in the development of preparative separation techniques for the saxitoxins were 1) the employment of carboxylate cation exchange resins by Schantz et al. (82) 2) the use of the polyacrylamide gel Bio-Gel P2 by Buckley and by Shimizu (5,78) and 3) the development by Buckley of an effective TLC system, including a new solvent mixture and a new visualization technique (83). The solvent mixture, designated by Buckley as "E", remains the best for general resolution of the saxitoxins. The visualization method, oxidation of the saxitoxins on silica gel TLC plates to fluorescent degradation products with hydrogen peroxide and heat, is an adaptation of the Bates and Rapoport fluorescence assay for saxitoxin in solution. Curiously, while peroxide oxidation in solution provides little or no response for the N-l-hydroxy saxitoxins, peroxide spray on TLC plates is a sensitive test for all saxitoxin derivatives with the C-12 gemdiol intact. 

Ion exchange (IX) is a very useful technique for the concentration, the purification and the separation of chemically similar metallic elements present in an aqueous solution. In its most popular form of application, the metal-bearing aqueous solution is passed through a bed of solid organic resin in a particulate form wherein the sorption of the metal ions on the resin takes place by ion-exchange reactions. The pregnant resin is washed free of the entrapped feed solution and then brought into contact with an eluant of suitable composition and volume so that the resin releases the metal ions back to the eluant. The ratio of the volume of the feed and that of the eluant determines the extent of concentration that can be achieved. Purification and separation are achievable if the resin is selective or specific with respect to the metal ions of interest in comparison to impurity ions. 

---