Molecular recognition capabilities

The main aim in host-guest chemistry is to construct molecular receptors by a self-assembly process so that such receptors could, to some extent, gain molecular recognition capability. The goal of such molecular recognition capability is to either mimic or block a biological effect caused by molecular interactions [157]. 

The calorimetric binding isotherms of the carbamoylated quinine and quinidine selectors clearly reveal that the heats released upon binding are strongly different for 5- and R-enantiomers of DNB-Leu, which is commensurate with the remarkable enantioselective molecular recognition capability of these selectors (Figure 1.14a,b). As can be seen from Table 1.4, the binding constants for R- and 5-enantiomers differ by about one order of magnitude in case of the carbamate-type selectors. Furthermore,... 

As mentioned above, some naturally occurring cyclic hosts that possess molecular recognition capabilities were known before crown ethers (the first artificial host molecules) were discovered. For example, the cyclic oligopeptide valinomycin and the cyclic oligosaccharide cyclodextrin were found to bind to specific guest molecules. The chemical modification of cyclodextrin was particularly well-researched, and artificially modified cyclodextrins became one of the most important compoimds used in host-guest chemistry. 

In principle, nanotubes with the Cig inside extract any lipophilic molecule. This ability to sequester lipophilic molecules can be viewed as a generic type of extraction selectivity, which might be useful in some apphcations. However, nanotubes that have molecular-recognition capability and extract only one particular molecule from solution might also be useful. We have shown that antibody-functionalized nanotubes can provide the ultimate in extraction selectivity—the extraction of one enantiomer of a chiral drug molecule. 

Native enzymes, which can spatially and chemically recognize substrate molecules, are powerful catalytic systems in many biochemical processes under mild reaction conditions. The preparation of artificial enzymatic catalysts with the capability of molecular recognition capability, by a molecular-imprinting method, which creates cavities with a similar shape and size to the template molecule in polymer matrices has been developed [1-14]. The technique has been mainly established in the field of analytical chemistry - molecular receptors [15-23], chromatographic separations [24-28], fine chemical sensing [29-33]. All of the methods rely on the selective adsorption of target molecules on imprinted adsorption sites. The number of papers reported per year on molecular imprinting is summarized in Fig. 22.1. 

Natural polymers remain an inspiration and provide considerable stimulation for researchers of artificial intelligent materials and systems. For example, antibodies and enzymes provide the molecular recognition capabilities used so magnificently by nature. Macromolecules are also the basis of that most useful of actuator systems muscles. Furthermore, it is the generation and transmission of electrical signals that regulate the processes behind the formation and operation of these biosystems. 

Treatment of a number of covalent polymers substituted with molecular recognition capability with suitable guests leads to chiral induction. The same crown ether-amino acid complementary pair described for the rosettes above was employed in the form of crown-ether pendant cis-transoidai poly(phenylacetylene). When the achiral polymer is treated with amino acids (in the form of their hydroperchlorate salts in acetonitdle) a large induced CD signal is observed in the backbone of the polymer. The polymer is sensitive to small enantiomeric excesses in the amino acid, as little as 0.005% enantiomeric excess of alanine can be detected. In a similar vein, c/5-transoidal poly(carboxyphenylacetylene) shows induced circular dichroism when treated with nonracemic chiral amines In addition, the system displays chiral memory, in that treatment of the complex with achiral amino alcohols results in retention of the chiral polymer backbone. 

The molecular recognition capabilities of polyelectrolyte multilayers have also been investigated by Laschewesky [55], while imprinted films have been grown on membrane surfaces in approaches similar to the phase inversion method for preparing a membrane imprinted with theophylline. Wang et al. [56] adopted an acrylonitri-le/dithiocarbamoyl-methylstyrene copolymer (Fig. 16) to effect separation of caffeine from the theophylline-imprinted membrane. 

Although this concept was only recently articulated as a general approach to the synthesis of chemical species exhibiting molecular recognition capabilities, many of the principles and practices that characterize DCC had been in place for several decades. DCC may be viewed as the intersection of two pre-edsting approaches to synthesis thermodynamically controlled templated synthesis and combinatorial chemistry. 

Moisture absorptivity, 17-45 Molar conductivity AMPS, 305-6 PAMPS, 305-6 temperature dependence, 306 Molecular imprinting resins, 293, 295, 296 Molecular imprinting technique, 289, 290, 291 Molecular orientation, 395 Molecular permeation, 135 Molecular recognition capability, 290 Molecular recognition information, 290 Molecular recognition molecules, 289 Molecular recognition sensor, 296 Molecular stifiening concept, 38 Molecular valves, stimuli-responsive sur ce as, 135-6... 

A number of physical devices with chemical sensitivity have been developed previously, including the quartz crystal microbalance (QCM) and other acoustic wave devices, semiconductor gas sensors, and various chemically sensitive field effect transistors. However, based on their intrinsic detection principles, most of the known solid state chemical sensors are not selective, i.e., they respond to more than one or a few chemical species. There is an urgent demand for new families of selective, microscope sensors that can eventually be integrated into microelectronic circuits. We have embarked on a program aimed at the design of conceptually new microporous thin films with molecular recognition capabilities. On the surface of chemical sensors, these membranes will serve as "molecular sieves that control access of selected target molecules to the sensor surface. 

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