Hydrophobic supports

Adsorbents for biomacromolecules such as proteins have special properties. First, they need to have large pore sizes. A ratio of pore radius to molecule radius larger than 5 is desirable to prevent excessive diffusional hindrance (see Intraparticle Mass Transfer in this section). Thus, for typical proteins, pore radii need to be in excess of 10-15 nm. Second, functional groups for interactions with the protein are usually attached to the adsorbent backbone via a spacer arm to provide accessibility. Third, adsorbents based on hydrophilic structures are preferred to limit nonspecific interactions with the adsorbent backbone and prevent global unfolding or denaturation of the protein. Thus, if hydrophobic supports are used, their surfaces are usually rendered hydrophilic by incorporating hydrophilic coatings such as dextran or polyvinyl alcohol. Finally, materials stable in sodium hydroxide solutions (used for clean-in-place) are... 

J. Xu et al. [283] have shown that immobilization of enzymes can be done using a specially designed composite membrane with a porous hydrophobic layer and a hydrophilic ultrafiltration layer. A polytetrafluoroethylene (PTFE) membrane with micrometer pores as an excellent hydrophobic support for immobilization was employed for the porous hydrophobic layer, and a biocompatible material of polyvinyl alcohol (PVA) which provided a favourable environment to retain the lipase activity was used to prepare the hydrophilic... 

It is well known that Nafion ionomer contains both hydrophobic and hydrophilic domains. The former domain can facilitate gas transport through permeation, and the latter can facilitate proton transfer in the CL. In this new design, the catalyst loading can be further reduced to 0.04 mg/cm in an MEA [10,11]. However, an extra hydrophobic support layer is required. This thin, microporous GDL facilitates gas transport to the CL and prevents catalyst ink bleed into the GDL during applications. It contains both carbon and PTFE and functions as an electron conductor, a heat exchanger, a water removal wick, and a CL support. 

Binding to cation or anion exchanger at distinct pH and ionic strength or to hydrophobic supports (binding maybe as useful as no binding if impurities show the opposite behavior)... 

The type of support chosen can have an impact on the facility with which nucleophilic cleavage takes place. Polystyrene, a very hydrophobic support, is difficult to perfuse with small ions such as hydroxide, and for this reason the saponification of poly-styrene-bound esters usually proceeds more slowly than the corresponding solution reaction. Tentagel, polyacrylamides, or other more hydrophilic supports are generally a better choice if saponifications or other reactions involving small ions are to be performed. 

Wittig reactions can also be performed with support-bound phosphorus ylides. Polystyrene-bound alkylphosphonium salts have been prepared from the corresponding alkyl mesylates or halides and trialkyl- or triarylphosphines (Figure 5.8 [60,80]). Because polystyrene is a hydrophobic support, salt formation does not proceed smoothly and quaternization of phosphines generally requires forcing conditions. The... 

The most common synthesis of sulfonic esters, which can also be conducted on insoluble supports, is the sulfonylation of alcohols with sulfonyl chlorides under basic reaction conditions. Several examples of the sulfonylation of support-bound alcohols and of the reaction of support-bound sulfonyl chlorides with alcohols have been reported (Table 8.11). For the preparation of highly reactive sulfonates, bases of low nucleophilicity, such as DIPEA or 2,6-lutidine, should be used to prevent alkylation of the base by the newly formed sulfonate. This potential side reaction is, however, less likely to occur on cross-linked polystyrene than in solution, because quaternization on hydrophobic supports only proceeds sluggishly (see Section 10.2 and [155]). 

Carbamates are by far the most common type of amine protection used in solid-phase synthesis. Various types of carbamate have been developed that can be cleaved under mild reaction conditions on solid phase. Less well developed, however, are techniques that enable the protection of support-bound amines as carbamates. Protection of amino acids as carbamates (Boc or Fmoc) is usually performed in solution using aqueous base (Schotten-Baumann conditions). These conditions enable the selective protection of amines without simultaneous formation of imides or acylation of hydroxyl groups. Unfortunately, however, Schotten-Baumann conditions are not compatible with insoluble, hydrophobic supports. Other bases and solvents have to be used in order to prepare carbamates on, for example, cross-linked polystyrene, and more side reactions are generally observed than in aqueous solution. 

Amides with electron-withdrawing substituents can be sufficiently labile towards nucleophilic attack to enable their use as protective groups. This is the case, for example, with trifluoro- [102,290] and trichloroacetamides [163], which are readily hydrolyzed under mild conditions (Figure 10.13). Suitable nucleophiles are hydrazine [291], aliphatic amines, and hydroxide, but if a hydrophobic support has been chosen, it must be borne in mind that the reactivity of alkali metal hydroxides will be reduced because of poor diffusion into the support. Amides of electron-poor amines (e.g. anilides) can also be readily cleaved by nucleophiles [292],... 

The formation of charged molecules within hydrophobic supports does not proceed as smoothly as in polar solvents. For instance, high reaction temperatures are required to quaternize polystyrene-bound phosphines [335,336], and the N-benzylation of pyri-dines with Merrifield resin also proceeds sluggishly [37]. Quaternization of tertiary... 

Most of these procedures are incompatible with common linkers, and are therefore unsuitable for the transformation of support-bound substrates into carboxylic acids. A more versatile approach for this purpose is the saponification of carboxylic esters. Saponifications with KOH or NaOH usually proceed smoothly on hydrophilic supports, such as Tentagel [19] or polyacrylamides, but not on cross-linked polystyrene. Esters linked to hydrophobic supports are more conveniently saponified with LiOH [45] or KOSiMe3 in THF or dioxane (Table 13.11). Alternatively, palladium(O)-mediated saponification of allyl esters [94] can be used to prepare acids on cross-linked polystyrene (Entries 9 and 10, Table 13.11). Fmoc-protected amines are not deprotected under these conditions [160],... 

Dihydropyrroles have recently become readily available by ring-closing metathesis. For this purpose, N-acylated or N-sulfonylated bis(allyl)amines are treated with catalytic amounts of a ruthenium carbene complex, whereupon cyclization to the dihydropyrrole occurs (Entries 6 and 7, Table 15.3 [30,31]). Catalysis by carbene complexes is most efficient in aprotic, non-nucleophilic solvents, and can also be conducted on hydrophobic supports such as cross-linked polystyrene. Free amines or other soft nucleophiles might, however, compete with the alkene for electrophilic attack by the catalyst, and should therefore be avoided. 

In these kinds of systems, the polarization phenomenon is effective at the two interfaces involved (see also Sect. 2.3.2). Specifically, in membrane systems comprising two ITIES, this behavior is achieved when the membrane contains a hydrophobic supporting electrolyte and the sample aqueous solution (the inner one) contains hydrophilic supporting electrolytes, and there is no common ion between any of the adjacent phases. In this case, the potential drop cannot be controlled individually and the processes taking place at both interfaces are linked to each other by virtue of the same electrical current intensity. 

Separations in two-phase systems with one immobilized interface(s) are much newer. The first paper on membrane-based solvent extraction (MBSE) published Kim [4] in 1984. However, the inventions of new methods of contacting two and three liquid phases and new types of liquid membranes have led to a significant progress in the last forty years. Separations in systems with immobilized interfaces have begun to be employed in industry. New separation processes in two- and three-phase systems with one or two immobilized L/L interfaces realized with the help of microporous hydrophobic wall(s) (support) are alternatives to classical L/L extraction and are schematically shown in Figure 23.1. Membrane-based solvent extraction (MBSE) in a two-phase system with one immobilized interface feed/solvent at the mouth of microspores of hydrophobic support is depicted in Figure 23.1a and will be discussed... 

Matrix mechanisms of sodium Urushi and PVC/ISFETs. The electrochemical characteristics, such as linear response range, sensitivity, selectivity and response time of the Urushi matrix ISFETs are similar to those of the PVC matrix ISFETs. The reason of the same characteristics is discussed from the standpoint of matrix mechanisms as follows. The obtained results indicate that these characteristics are mainly determined not by polymeric matrix materials but by sodium-sensing materials, including the membrane solvent (NPOE etc.). Therefore, it is considered that the polymeric matrix materials, such as PVC and Urushi only act as a hydrophobic support polymer and that the major part of surface of the matrix membrane should be covered with the membrane solvent containing the Na ionophore. 

Separation and disposal of precipitate, coprecipitation, new contaminants added, decreased effectiveness with decreased concentration of target species, limited selectivity options Selectivity based on ion charge, new contaminants added, decreased selectivity with decreased concentration of target species, large space requirements, hydrophobic support, slow kinetics... 

Glass-fiber filters and polyvinylidene difluoride (PVDF) membranes have been the primary sequencing supports for gas-phase and liquid-pulse Edman sequencers. As an alternative support, the Hewlett-Packard sequencer has used a biphasic column system utilizing a hydrophobic support to which the protein/peptide is applied. For sequencing membrane-bound samples, a membrane-compatible column was recentiy introduced. As a C-terminal sequencing support, Bailey (1) has utilized Zitex, a porous teflon membrane. 

Immobilization of lipases on hydrophobic supports has the potential to (1) preserve, and in some cases enhance, the activity of lipases over their free counterparts (2) increase their thermal stability (3) avoid contamination of the lipase-modified product with residual activity (4) increase system productivity per unit of lipase employed and (5) permit the development of continuous processes. As the affinity of lipases for hydrophobic interfaces constitutes an essential element of the mechanism by which these enzymes act, a promising reactor configuration for the use of immobilized lipases consists of a bundle of hollow fibers made from a microporous hydrophobic polymer (137). 

Most often, pentanol or butyronitrile is used as the stationary phase loaded onto a hydrophobic support such as silanized silica. 

---