Large molecules, adsorption

Probing large molecule adsorption stearate monolayers on calcite... 

Activated carbons for use in Hquid-phase appHcations differ from gas-phase carbons primarily in pore size distribution. Liquid-phase carbons have significantly more pore volume in the macropore range, which permits Hquids to diffuse more rapidly into the mesopores and micropores (69). The larger pores also promote greater adsorption of large molecules, either impurities or products, in many Hquid-phase appHcations. Specific-grade choice is based on the isotherm (70,71) and, in some cases, bench or pilot scale evaluations of candidate carbons. 

The prepared MAC adsorbents were tested for benzene, toluene, 0-, m-, p-xylene, methanol, ethanol, iso-propanol, and MEK. The modified content of all MACs was 5wt% with respect to AC. The specific surface areas and amounts of VOC adsorbed of MACs prepared in this study are shown in Table 1. The amounts of VOC adsorbed on 5wt%-MAC with acids and alkali show a similar tendency. However, the amount of VOC adsorbed on 5wt%-PA/AC was relatively large in spite of the decrease of specific surface area excepting in case of o-xylene, m-xylene, and MEK. This suggests that the adsorption of relatively large molecules such as 0-xylene, m-xylene, and MEK was suppressed, while that of small molecules was enhanced. It can be therefore speculated that the phosphoric acid narrowed the micropores but changed the chemical nature of surface to adsorb the organic materials strongly. 

Another factor producing an apparent decrease in the activity of disperse catalysts is steric hindrance. In reactions involving relatively large molecules, not aU of the inner surface area of the catalyst may by accessible for these molecules, so that the true working surface area is smaller than that measured by BET or hydrogen adsorption. 

One of the most attractive roles of liquid liquid interfaces that we found in solvent extraction kinetics of metal ions is a catalytic effect. Shaking or stirring of the solvent extraction system generates a wide interfacial area or a large specific interfacial area defined as the interfacial area divided by a bulk phase volume. Metal extractants have a molecular structure which has both hydrophilic and hydrophobic groups. Therefore, they have a property of interfacial adsorptivity much like surfactant molecules. Adsorption of extractant at the liquid liquid interface can dramatically facilitate the interfacial com-plexation which has been exploited from our research. 

In exclusion chromatography, the total volume of mobile phase in the column is the sum of the volume external to the stationary phase particles (the void volume, V0) and the volume within the pores of the particles (the interstitial volume, Vj). Large molecules that are excluded from the pores must have a retention volume VQ, small molecules that can completely permeate the porous network will have a retention volume of (Vo + Fj). Molecules of intermediate size that can enter some, but not all of the pore space will have a retention volume between VQ and (V0 + Fj). Provided that exclusion is the only separation mechanism (ie no adsorption, partition or ion-exchange), the entire sample must elute between these two volume limits. 

Hydrophilic peptides and proteins are frequently large molecules they may enter the brain by carrier-mediated transport, receptor-mediated transcytosis, or by adsorptive-mediated transcytosis. Small peptides, such as di- and tripeptides are transported by the specific transporters, PepTl and PepT2, but neither of them is present at the BBB. Nevertheless, there is saturable brain uptake of the tripeptide glutathione and of several opioid peptides, suggesting that specific transporters, as... 

Carbon black adsorbed OLOA 1200 very strongly, eventually picking up 5% of its weight in dispersant. The first 2% adsorbed almost instantly, but additional increments adsorbed more and more slowly (see Figure 5). Such time-dependence in adsorption of large molecules is quite common (15), but is seldom studied. The adsorption isotherms determined after 48 hours of tumbling at 25°... 

Wall-adsorption variance. Analyte-wall interactions are possible in fused silica capillaries depending on the characteristics of the wall and the analytes. Usually it concerns an ionic interaction mechanism, but sometimes hydrophobic interactions are also possible. Wall adsorption is frequently observed in the analysis of large molecules [26,33], but is also observed in separations of small ions [34]. The variance due to wall adsorption is given by the following expression [29] ... 

When particles or large molecules make contact with water or an aqueous solution, the polarity of the solvent promotes the formation of an electrically charged interface. The accumulation of charge can result from at least three mechanisms (a) ionization of acid and/or base groups on the particle s surface (b) the adsorption of anions, cations, ampholytes, and/or protons and (c) dissolution of ion-pairs that are discrete subunits of the crystalline particle, such as calcium-oxalate and calcium-phosphate complexes that are building blocks of kidney stone and bone crystal, respectively. The electric charging of the surface also influences how other solutes, ions, and water molecules are attracted to that surface. These interactions and the random thermal motion of ionic and polar solvent molecules establishes a diffuse part of what is termed the electric double layer, with the surface being the other part of this double layer. 

The stability of solid particles or liquid drops can be also controlled by using large molecules (polymers). The addition of a polymer will result in adsorption in a solid or penetration in a liquid (Figure 7.9). 

Polymer adsorption tends to be indiscriminate. The large molecules become attached to essentially any available surface unless strongly repelled from it. 

In semi-crystalline polymers the interaction of the matrix and the tiller changes both the structure and the crystallinity of the interphase. The changes induced by the interaction in bulk properties are reflected by increased nucleation or by the formation of a transcrystalline layer on the surface of anisotropic particles [48]. The structure of the interphase, however, differs drastically from that of the matrix polymer [49,50]. Because of the preferred adsorption of large molecules, the dimensions of crystalline units can change, and usually decrease. Preferential adsorption of large molecules has also been proved by GPC measurements after separation of adsorbed and non-attached molecules of the matrix [49,50]. Decreased mobility of the chains affects also the kinetics of crystallization. Kinetic hindrance leads to the development of small, imperfect crystallites, forming a crystalline phase of low heat of fusion [51]. 

The original treatment of this type of displacement isotherm was developed by Flory and Huggins separately, back in 1942. They developed the isotherm for adsorption of large molecules (polymers). However, applicability to small molecules (e.g., ions) displacing only few water molecules has been proved. 

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