Supramolecular Polymers and Assemblies. Andreas Winter

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СКАЧАТЬ representation of the synthesis of polyrotaxanes with stopper moieties within the polymers main chain.Figure 6.32 Schematic representation of the polystyrene‐based poly(pseudo)rotaxanes.Figure 6.33 Schematic representation of the hydrophilic macromolecular host 39 and the hydrophilic guest 40 that self‐assembled into a pH‐responsive supramolecular amphiphile; the amphiphile could be used as a nanocontainer for the encapsulation and controlled release of hydrophobic molecules, such as Nile red. Source: Ji et al. [121], © 2012 American Chemical Society.Figure 6.34 Schematic representation of the formation of an amphiphilic supramolecular diblock copolymer from 29 and 31 that assembled further into nanostructures depending on the length ratio of the constituent blocks (l_sp: length of the supramolecular block, l_cp: length of the covalent block). Source: Ji et al. [122], © 2013 John Wiley and Sons.

      7 Chapter 7Figure 7.1 Schematic representation of the generalized CB[n] synthesis via co‐condensation of 1 with formaldehyde under acidic conditions. The dimensions of different CB[n] representatives are listed [5]. The ball‐stick representation of the solid‐state structure of CB[8] is also shown. Source: Kim et al. [4], © 2000 American Chemical Society.Figure 7.2 Schematic representation of the various exclusion and inclusion complexes of CB[n]s. Source: Barrow et al. [16].Figure 7.3 Schematic representation of the formation of supramolecular polymers via complexation of BB‐ or ABBA‐type monomers by a CB[n] host. Source: Redrawn from Yang et al. [33], © 2015 American Chemical Society.Figure 7.4 Schematic representation of the formation of a surface‐anchored supramolecular polymer (counterions omitted for clarity). Source: Kim et al. [53], © 2004 American Chemical Society.Figure 7.5 Schematic representation of the formation of the supramolecular polymer {4@CB[8]}_n; the assembly into 1 : 1 or 2 : 2 species is prevented due to steric and electronic constraints, respectively. Source: Liu et al. [55], © 2010 John Wiley and Sons.Figure 7.6 Schematic representation of a supramolecular polymer based on metal‐to‐ligand coordination and host–guest complexation. Source: Liu et al. [56], © 2013 The Royal Chemical Society.Figure 7.7 (a) Schematic representation of the bifunctional monomer 6 (counterions were omitted for clarity). (b) Side view of the X‐ray single crystal structure of {6@CB[8]}_n. Source: del Barrio et al. [57], © 2013 American Chemical Society.Figure 7.8 (a) Schematic representation of the ditopic monomers 7 to 9. (b) Schematic representation of the linear supramolecular polymer {9@CB[8]}_n. Source: Liu et al. [59], © 2013 John Wiley and Sons.Figure 7.9 Schematic representation of the imidazolium‐containing guests 10 and 11. (a) Schematic representation of the step‐wise self‐assembly of 11 and CB[8] into linear polymer chains and, subsequently, fibrous aggregates. (b) Representative AFM images of the crystalline nanostructures obtained from 10/CB[8] (left) and 11/CB[8] (right). Source: Barrio et al. [62]. Figure reproduced with kind permission; © 2019 American Chemical Society. Licensed under CC BY 4.0.Figure 7.10 (a) Schematic representation of the self‐assembly of 12 and CB[8] into 2 : 2 dimers and linear polymers due to the formation of H‐ or J‐type aggregates within the hosts' cavities. (b) Representation of the structure of oligomeric {12@CB[8]}_n according to molecular modeling. Source: Xu et al. [63], © 2011 The Royal Chemical Society.Figure 7.11 (a) Schematic representation of the homoditopic monomer 13. (b) Schematic representation of the proposed 2 : 1 binding mode. (c) AFM–SMFS curves of the supramolecular polymer {10@CB[8]}_n and the Gaussian fitting thereof. Source: Tan et al. [60], © 2013 Royal Society of Chemistry.Figure 7.12 (a) Schematic representation of the formation of a cyclic 1 : 1 complex via a ring‐chain equilibrium pathway. (b) Schematic representation for the inhabitation of protein complexation due to the formation of the highly stable cyclic complex. Source: Ramaekers et al. [67], © 2013 Royal Society of Chemistry.Figure 7.13 (a) Schematic representation of the formation of a discrete 2 : 3 complex and (b) a 2D supramolecular organic framework due to radical dimerization stabilized by CB[8]. Source: Zhang et al. [72], © 2014 Royal Society of Chemistry.Figure 7.14 (a) Schematic representation of the self‐assembly of the MV˙⁺ radical cation and CB[8] into a 2 : 1 complex. (b) Schematic representation of the hexacationic ditopic guest 14. Source: Redrawn from ref. Yin et al. [76], © 2013 Chinese Chemical Society.Figure 7.15 Schematic representation of the proposed equilibrium for the self‐assembly of a bis‐CB[10] derivative with a bis‐adamantyl guest into discrete complexes and linear supramolecular polymers. Source: Nally and Isaacs [85], © 2009 Elsevier.Figure 7.16 Schematic representation of the synthesis of CyP_nTD[n] macrocycles. The solid‐state structure of CyP₄TD[4], as determined by single crystal X‐ray analysis, as well as the cavity dimensions of the CyP_nTD[n] derivatives are also shown. Source: Wu et al. [86], © 2017 Royal Society of Chemistry.Figure 7.17 Schematic representation of the formation of a supramolecular polymer network with AIE behavior. A representative TEM image of the polymer particles is also depicted. Source: Wu et al. [88], © 2018 Royal Society of Chemistry. Figure reproduced with kind permission; © 2018 The Royal Chemical Society.Figure 7.18 Schematic representatio of the two‐step self‐assembly of the TPE dyes 15 and 16 into cubic or spherical nanostructures, respectively. Representative TEM images visualizing these nanostructures are also depicted. Source: Li et al. [90]. Figure reproduced with kind permission; © 2018 Wuiley‐VCH.Figure 7.19 Schematic representation of the self‐assembly of 2 : 1 heterotrimers due the formation of a CT complex within the CB[8] cavity; (a–c) three applications of this particular interaction using polymeric building blocks are also shown. Source: Rauwald and Scherman [96], © 2008 John Wiley and Sons.Figure 7.20 Schematic representation for the formation of a supramolecular ABA‐type triblock copolymer. Source: Zayed et al. [98], © 2014 Royal Society of Chemistry.Figure 7.21 Schematic representation of the step‐wise, self‐assembly of supramolecular micelles that could be used for the controlled release of doxorubicin, as a model drug. The release, as a function of the added reducing agent, is also shown. Source: Zhao et al. [99], © 2014 Royal Society of Chemistry.Figure 7.22 Schematic representation of the temperature‐triggered formation of double‐layered vesicles from supramolecular lipid–peptide conjugates. Source: Loh et al. [102], © 2014 Royal Society of Chemistry.Figure 7.23 Schematic representation of the stepwise formation of vesicles from an initial mixed micellar system by CB[8]‐triggered self‐sorting. Source: Mondal et al. [104], © 2014 American Chemical Society.

      8 Chapter 8Figure 8.1 Schematic representation of the macrocyclic hosts calix[n]arene and resorcin[n]arene (R denotes any substituent; whereas, n and m = n − 3 refer to the number of phenyl moieties within the macrocycle).Figure 8.2 Schematic representation of the tetraurea‐functionalized calix[4]arene (a) and of its dimer with an encapsulated small guest molecule (b) [21]. Source: Redrawn from Dalcanale and Pinalli [19], © 2015 Springer Nature.Figure 8.3 Schematic representation of the self‐assembly of calix[4]arene dimers 2 into polycaps [21]. Source: Redrawn from Dalcanale and Pinalli [19], © 2015 Springer Nature.Figure 8.4 Schematic representation of the depolymerization of a polycap in the presence of a dimeric capsule into a dumbbell‐shaped 2 : 1 complex [21]. Source: Redrawn from Dalcanale and Pinalli [19]. © 2015 Springer Nature.Figure 8.5 Schematic representation of different polycaps derived from homo‐ or heteroditopic bis‐calixarenes (black calixarenes are equipped with aryl ureas, gray calixarenes carry sulfonyl ureas). Source: Castellano et al. [24], © 1998 American Chemical Society.Figure 8.6 (A) Photomicrographs of a typical Schlieren texture observed from a LC polycap in CHCl₃ (a) and p‐difluorobenzene (b) as viewed between crossed polarizers. (B) Laser confocal microscopy images of fibers assembled from the LC phases of the polycap in CHCl₃ either by sample shearing (a) or fiber pulling from the sample (b). Source: Castellano et al. [25]. Figure reproduced with kind permission; © 1999 Wiley‐VCH.Figure 8.7 Schematic representation of the bis‐calixarene 3 comprising a pH‐sensitive dipeptide linker that could be used to switch between a soluble and insoluble form of the resulting polycap. Source: Redrawn from Xu et al. [27], © 2003 American Chemical Society.Figure 8.8 Schematic representation of the two‐step assembly of a supercap by (a) calixarene dimerization in an apolar solvent and (b) binding of СКАЧАТЬ