Silica poly

Figure Bl.19.30. Height and friction images of a spin-cast polystyrene-poly(methyl methacrylate) blend obtained with (a) gold and (b) silica probes under perfluorodecalin. Note the reversal of frictional contrast and the high spatial resolution. (Taken from [142], figure 7.)...

Solid-phase microextractions also have been developed. In one approach, a fused silica fiber is placed inside a syringe needle. The fiber, which is coated with a thin organic film, such as poly(dimethyl siloxane), is lowered into the sample by depressing a plunger and exposed to the sample for a predetermined time. The fiber is then withdrawn into the needle and transferred to a gas chromatograph for analysis. 

Capillary Tubes Figure 12.42 shows a cross section of a typical capillary tube. Most capillary tubes are made from fused silica coated with a 20-35-)J,m layer of poly-imide to give it mechanical strength. The inner diameter is typically 25-75 )J,m, which is smaller than that for a capillary GC column, with an outer diameter of 200-375 )J,m. 

Calcium carbonate is controlled with poly(maleic acid) (26) and organic phosphonates. Dispersants designed to control silica and magnesium silicate (7,27,28) have been introduced. 

The tnmethylsilyl enol ether of 1 mdanone (3 2 mmol) in 2 mL of methylene chlonde is added to a mixture of xenon difluonde (4 mmol) and a catalytic amount of pyndimum poly (hydrogen fluonde) m 5 mL of methylene chlonde The mixture IS stured at 0 C for 2 h and poured into dilute sodium bicarbonate solution, tlie organic layer is separated and dned After concentration and column chromatogra phy (silica gel, hexanes), 2-fluoro-1 -mdanone (mp, 59 C) is obtamed in 87% yield... 

A SEC material should be hydrophilic if it is to be used for biological applications. One such material, introduced by PolyLC in 1990 (8), is silica with a covalently attached coating of poly(2-hydroxyethyl aspartamide) the trade name is PolyHYDROXYETHYL Aspartamide (PolyHEA). This material was evaluated for SEC of polypeptides by P.C. Andrews (University of Michigan) and worked well for the purpose (Fig. 8.1). Because formic acid is a good solvent for polypeptides, Dr. Andrews tried a mobile phase of 50 mM formic acid. The result was a dramatic shift to a lower fractionation range for both Vq and V, (Fig. 8.2) to the point that V, was defined by the elution position of water. 

PMMA, on the unmodified porous glass and silica gel, and the universal calibration curves for polystyrenes and poly(methyl methacrylates) did not coincide (10,12,19). 

The Zincke reaction has also been adapted for the solid phase. Dupas et al. prepared NADH-model precursors 58, immobilized on silica, by reaction of bound amino functions 57 with Zincke salt 8 (Scheme 8.4.19) for subsequent reduction to the 1,4-dihydropyridines with sodium dithionite. Earlier, Ise and co-workers utilized the Zincke reaction to prepare catalytic polyelectrolytes, starting from poly(4-vinylpyridine). Formation of Zincke salts at pyridine positions within the polymer was achieved by reaction with 2,4-dinitrochlorobenzene, and these sites were then functionalized with various amines. The resulting polymers showed catalytic activity in ester hydrolysis. ... 

Figure 12.18 LC-SFC analysis of mono- and di-laurates of poly (ethylene glycol) ( = 10) in a surfactant sample (a) normal phase HPLC trace (b) chromatogram obtained without prior fractionation (c) chromatogram of fraction 1 (FI) (d) chromatogram of fraction 2 (F2). LC conditions column (20 cm X 0.25 cm i.d.) packed with Shimpak diol mobile phase, w-hexane/methylene chloride/ethanol (75/25/1) flow rate, 4 p.L/min UV detection at 220 nm. SFC conditions fused-silica capillary column (15 m X 0.1 mm i.d.) with OV-17 (0.25 p.m film thickness) Pressure-programmed at a rate of 10 atm/min from 80 atm to 150 atm, and then at arate of 5 atm/min FID detection. Reprinted with permission from Ref. (23).

D.N. Kumar, J.D. Bhawalkar, P.N. Prasad, Solid-state cavity lasing from poly(/>-phenylencvinyl-ene)-silica nanocompositc bulk. Applied Optics 1998, 37, 510. 

A mixture of powdered poly(vinyl chloride), cyclohexanone as solvent, silica, and water is extruded and rolled in a calender into a profiled separator material. The solvent is extracted by hot water, which is evaporated in an oven, and a semiflexible, microporous sheet of very high porosity ( 70 percent) is formed [19]. Further developments up to the 75 percent porosity have been reported [85,86], but these materials suffer increasingly from brittleness. The high porosity results in excellent values for acid displacement and electrical resistance. For profiles, the usual vertical or diagonal ribs on the positive side, and as an option low ribs on the negative side, are available [86],... 

It has been outlined by several authors that the single macromolecule may be irreversibly bound because of the large number of weakly interacting segments. The first papers on the construction of polymer-coated silica adsorbents involved the physical adsorption of water-soluble polymers. Polyethylene oxides [28, 29] and poly-/V-vinylpyrrolidone [30] are examples of the stationary phases of this type. 

The drawback of the described adsorbents is the leakage of the bonded phase that may occur after the change of eluent or temperature of operation when the equilibrium of the polymer adsorption is disturbed. In order to prepare a more stable support Dulout et al. [31] introduced the treatment of porous silica with PEO, poly-lV-vinylpyrrolidone or polyvinylalcohol solution followed by a second treatment with an aqueous solution of a protein whose molecular weight was lower than that of the proteins to be separated. Possibly, displacement of the weakly adsorbed coils by the stronger interacting proteins produce an additional shrouding of the polymer-coated supports. After the weakly adsorbed portion was replaced, the stability of the mixed adsorption layer was higher. 

The chemical adsorption of a relatively high molecular weight neutral polymer (poly(succinimide), M = 13000) on aminopropyl-Vydac 101 TP silica gel was applied by Alpert [47, 48] to prepare a reactive composite support for use in cation-exchange [47] and hydrophobic-interaction [48] chromatography of pro-... 

Alpert has shown [47] that poly(succinimide)-silica can be further hydrolyzed to poly (aspartic acid)-silica or condensed with [3-alanine in aqueous solution to form a covalently bonded copolymer of 2-carboxyethyl aspartamide and aspartic acid. The content of carboxyl groups generated by this way has not been quantified directly, but the cation-exchange hemoglobin capacity has been measured for a series of the packings. Thus, the optimal concentration of poly(succinimide) used in the synthesis was found to be 2 5%. 

Protein mixtures were well resolved on poly(aspartic acid)-silica columns using 0.05 mol/1 phosphate buffer, pH 6.0 and a gradient of sodium chloride from 0 to 0.6 mol/1. The columns displayed a high capacity and selectivity. Figure 3 shows the separation of several standard proteins with isoelectric points ranging from 4.7 to over 11. Peaks are sharp and show minimal tailing. The poly(aspartic acid) coating was quite stable the columns lasted for hundreds of hours of use without decrease in efficiency and capacity. 

A series of bonded poly(alkyl aspartamide) coatings was prepared on silica by analogy to the method described above. Poly(succinimide) coating was reacted with n-alkyl- and arylalkylamines in dimethylformamide to yield a series of hydrophobic adsorbents. Poly(propyl aspartamide)-silica (PolyPROPYL A) showed the maximal reversible hydrophobic binding of hemoglobin among the Cl -C5... 

Fig. 4. HPHIC of standard proteins on the weak hydrophobic columns. The SynChro-pack PROPYL column was 25x0.41 cm Poly (alkyl aspartamid)-silicas were packed into 20 x 0.46 cm columns. Sample 25 pi containing 25 pg of each protein in buffer A. Buffer A 1.8 mol/1 ammonium sulphate + 0.1 mol/1 potassium phosphate, pH 7.0. Buffer B 0.1 mol/1 potassium phosphate, pH 7.0. Gradient 40-min linear 0-100% buffer B. Flow rate 1 ml/min. Detection A220 = 1-28 a.u.f.s. Peaks a = cytochrome C, b = ribonu-clease A, c = myoglobin, d = conalbumin, e = neochymotrypsin, / = a-chymotrypsin, g - a-chymotrypsinogen A [48]...

These carbonyl chloride-activated carriers are unstable on storage, so ligand coupling to them has to be undertaken immediately after chemisorption of the copolymer. To overcome this drawback, more stable activated carriers have been synthesized by treating aminopropyl-silicas with poly(p-nitrophenyl acrylate) and acetic anhydride. 

Immobilization of A and B blood group oligosaccharide haptens and preparation of immunoadsorbents with specificity to anti-A and anti-B antibodies has been carried out with the use of poly acrylate-coated PG (WPG-PA) [124]. Prespacered A and B-trisaccharide-fl-aminopropylglycosides were used for the synthesis. WPG-PA (1 g) quantitatively binds both haptens (2 pinole) whereas some other activated affinity supports (for example, CNBr-Sepharose 4B) do not. On the other hand, glycidoxypropyl-silica binds prespacered haptens completely but these materials reveal no specific adsorptivity. 

Mark and his co-workers reported the reinforcement of poly(dimethylsiloxane) networks by silica gel particles [1-6]. For example, bis(silanol)-terminated poly-(dimethylsiloxane) was reacted with tetraethoxysilane in the presence of acid-catalyst to produce the reinforced siloxane networks. The reaction proceeded homogeneously. The content of the silica filler can be controlled by the feed ratio of polysiloxane and tetraethoxysilane. 

As an organic polymer, poly(tetramethylene oxide) was also used for the preparation of ceramers. The mechanical properties in these cases were much improved in comparison with those for hybrids from polysiloxanes. In these poly (tetramethylene oxide)-silica hybrids, the effect of the number of functional triethoxysilyl groups was examined [13]. As shown in Fig. 2, more multifunctional organic polymer produced more crosslinked hybrid networks. This means that the more rigid the structure in the hybrids is, the higher the modulus and the lower swelling property. 

By using a similar procedure for the preparation of hybrids of silica, hybrids materials consisting of other metal oxides were also prepared by the group of Wilkes [15]. For example, titania was incorporated into organic polymers by using the chemically controlled condensation (CCC) method for the preparation of poly(tetramethylene oxide)-silica or poly(dimethylsiloxane)-silica hybrids. Especially, in the case of the hybrid with poly (tetramethylene oxide), the modulus or ultimate strength of the hybrid increased in the presence of titania component, as shown in Table 3. This phenomenon was explained by the catalytic ability of... 

Poly(arylene ether ketone) and poly(arylene ether sulfone) were also tried to be incorporated into the hybrids with silica gel by means of the sol-gel procedure [19, 20], For example, triethoxysilyl-terminated organic polymer was subjected to co-hydrolysis with tetraethoxysilane. A systematic change in mechanical and physical properties of the hybrid glass has been found with the content of organic polymer and the annealing temperatures. 

---