Page 571 - Carrahers_Polymer_Chemistry,_Eighth_Edition
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534                                                    Carraher’s Polymer Chemistry


                                                                   R      O
                                              O            CH 3
                                   O
                             O                O                      CH 3  O

                          R            CH 3                        O              O
                                         O      N            CH 3                      O
                                                                  O
                                                                   N
                                                                                    CH 3
                                       H C –                   OH
                                        3
                                           O
                                                                  N
                                                N
                                        O                                                  (16.23)
                                                                          CH 3
                                              O
                                                                                O
                                                          CH 3            O
                                                O
                                     O

                                O                                        O
                                                                  O
                                           CH 3

                                                                          CH 3
                                      R                             R


                    After polymerization, the MIP or functionalized polymer matrix is dried, ground, sieved, and
                 packed.
                    On the column, the eluding liquid is important. The liquid must dissolve the desired compound but
                 it should not be too good of a solvent or it will inhibit the release of the desired molecule allowing it to
                 interact with the template cavity. In the case of naproxen, there is a further consideration. Naproxen
                 has an acid function that was “templated” in the protonated form. Thus, acetic acid, along with THF
                 and heptane, was added to insure that the naproxen was present in the needed correct geometry.
                    As with most processes, MIPs have both positive and negative aspects. On the positive side, with
                 the correct choice of original polymer and solvent, almost any molecule can be employed as a tem-
                 plate, including much larger molecules. (This approach is not realistic for synthetic polymers where
                 the short-range geometry is varied and where the long-range geometry is not fixed. It might be fea-


                 sible for natural polymers where the structures are fixed.) Further, since the desired compound is
                 the one that is preferentially being attracted by the template site, it is the last to be eluded from the
                 column so that additional work is not needed to identify where the target molecules are. Increased
                 temperatures can also be employed, presumably to the range of 180ºC–200ºC so that high-temper-
                 ature isolations can be effected. In general, with the possible exception of the target compound, the
                 reagents are inexpensive so that such selective molecular sieves are relatively inexpensive.
                    On the negative side, there is excessive broadening of the elution band caused by a number of
                 features, including the heterogeneity of the imprint as noted before.
                    One problem with nanomolecules is ready alignment. On a molecular level, atomic force micros-
                 copy (AFM) and related tools can be used to align such individual or nanomolecules but this is
                 impractical on a large scale. Thus, strategies are being developed to accomplish this. One approach
                 for single-walled carbon nanotubes (SWNTs) is to physically or chemically anchor molecules onto
                 tubes and to have these anchors direct the nanomolecules into desired arrays or organizations.







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         K10478.indb   534                                                                    9/14/2010   3:43:08 PM
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