Polymers quadruple hydrogen bonds

As a scientific concept, supramolecular polymers have received increasing attention in recent years. The introduction of concepts from supramolecular chemistry in polymer science have led to the development of polymers in which the main chain is held together by noncovalent interactions such as hydrogen bonds, 7r-stacking, and coordination interactions. In the present chapter, we will discuss how the scientific developments in a specific class of supramolecular polymers — quadruple hydrogen-bonded supramolecular polymers — is now rapidly leading to applications that take advantage of the unique mechanical properties of these materials. 

J. H. K. K. Hirschbeig, F. H. Beijer, H. A. van Aert, P. C. M. M. Magusin, R. P. Sijbesma, E. W. Meijer, Supramolecular polymers from linear telechelic siloxanes with quadruple hydrogen bonded units , Macromolecules 1999, 32, 2696-2705. 

Hofmeier H, El-ghayoury A, Schenning APH, Schubert US (2004) New supramolecular polymers containing both terpyiidine metal complexes and quadruple hydrogen bonding units. Chem Commun 318-319... 

Sijbesma RP, Beijer FH, Brunsveld L, Folmer BJB, Hirschberg JHKK, Lange RFM, Lowe JKL, Meijer EW. Reversible polymers formed from self-complementary monomers using quadruple hydrogen bonding. Science 1997 278 1601-1604. 

Polymers Connected with Quadruple Hydrogen Bonds... 

Fig. 4 Supramolecular polymers due to quadruple hydrogen bonding between bifunctional ureidopyrimidinone derivatives [74]... 

Fig. 5 Films of intrinsically immiscible polymers with and without promotion by supramolecular linking, (a) Heterogeneous film of plain poly(butylmethacrylate) and polystyrene functionalized with 2,7-diamido-l,8-naphthyridine (DAN), (b) Transparent blend of poly(butylmethacrylate) functionalized with ureidoguanosine (UG) and polystyrene functionalized with DAN, thereby enabling quadruple hydrogen bonding of DAN and UG to facilitate polymer mixing. Reprinted with permission from [101]. Copyright 2006 American Chemical Society...

Schmuck, C. Wienand, W., Self-cranplementaiy quadruple hydrogen-bonding motifs as a functional principle From dimmc supramolecules to supramolecular polymers . Angew. Chem. Int. Ed. 2001, 40, (23), 4363 369. 

Lowe J.K.L., Meijer E.W., (1997), Reversible Polymers Formed from Self-Complementary Monomers Using Quadruple Hydrogen Bonding, Science 278, 1601. 

E. Meijer, Reversible polymers formed from selfrcomplementary monomers using quadruple hydrogen bonding. Science 278 (1997) 1601—1604. 

Fig. 1. Supramolecular polymers developed by (a) Lehn employing three-point hydrogen bonds between diamidopyridine and thymine residues and (b) Meijer employing self-complementary, quadruple hydrogen bonds, (c) A simplified schematic depicting the extended chain of repeating bisfunctional monomers fashioning the backbone of a supramolecular polymer.

Zimmerman and coworkers made use of complementary quadruple hydrogen-bonding complexes to form networks and blend two different side-chain functionalized polymers, poly(butyl methacrylate) (PBMA, marked in light blue) and PS (marked in red. Figure 5). The polymer blends were characterized by differential scanning calorimetry (DSC),... 

The quadruple hydrogen bond interaction of the biomimetic polymer discussed in the previous example was also studied in dimeric (UPy)2 complexes and supramolecular bridges comprising N (UPy)2 linkages between the AFM tip and the surface. The mpture forces for UPy moieties linked... 

Meijer et al. [64] described an unusual strategy to obtain metastable supramolecular polymer nanoparticles. Each nanoparticle arose from the collapse of a single polymer chain. This approach relied on a PNBE chain functionalized with a photoactivable quadruple hydrogen-bonding unit, which is able to create intramolecular cross-linking of single chains after deprotection. 

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