Hydrogen-bonded macrocycle-mediated dimerization for orthogonal supramolecular polymerization

• Wentao Yu,
• Zhiyao Yang,
• Chengkan Yu,
• Xiaowei Li and
• Lihua Yuan

Beilstein J. Org. Chem. 2025, 21, 179–188, doi:10.3762/bjoc.21.10

• materials. Keywords: hydrogen-bonded macrocycle; orthogonal self-assembly; shape-persistent; supramolecular polymer; Introduction Host–guest interactions, particularly those involving macrocycles as hosts [1], have found a myriad of applications in supramolecular chemistry [2][3][4] owing to their ability

• molecular weight on the solution concentration. Further, a change in solution viscosity would reflect a change in molecular weight during the polymerization process. Thus, the specific viscosity of the linear supramolecular polymer (Scheme 1c) in CHCl3/CH3CN (1:1, v/v) was determined at 298 K (Figure 7

• supramolecular polymer in CHCl3/CH3CN (1:1, v/v, 298 K) at variable concentration. Variable-concentration 1H NMR spectra of the supramolecular polymer: (a) 2.0 mM, (b) 4.0 mM, (c) 6.0 mM, (d) 8.0 mM, and (e) 10 mM. a) Chemical structures of H-bonded macrocycles H1, H2, and guest G1, and schematic representation

Adjusting the length of supramolecular polymer bottlebrushes by top-down approaches

• Tobias Klein,
• Franka V. Gruschwitz,
• Maren T. Kuchenbrod,
• Ivo Nischang,
• Stephanie Hoeppener and
• Johannes C. Brendel

Beilstein J. Org. Chem. 2021, 17, 2621–2628, doi:10.3762/bjoc.17.175

• straightforward adjustment of the length of polyethylene oxide (PEO)-based supramolecular polymer bottlebrushes (SPBs) in aqueous solutions. These cylindrical structures self-assemble via directional hydrogen bonds formed by benzenetrisurea (BTU) or benzenetrispeptide (BTP) motifs located within the hydrophobic

• established, commercial polymers in solution [17]. We recently reported the self-assembly of polyethylene oxide (PEO) polymers into cylindrical nanostructures, also called supramolecular polymer bottlebrushes (SPBs), based on the end group modification with hydrogen bond forming benzenetrisurea (BTU) and

Supramolecular polymers with reversed viscosity/temperature profile for application in motor oils

• Jan-Erik Ostwaldt,
• Christoph Hirschhäuser,
• Stefan K. Maier,
• Carsten Schmuck and
• Jochen Niemeyer

Beilstein J. Org. Chem. 2021, 17, 105–114, doi:10.3762/bjoc.17.11

• acid (GCP) or the aminopyridine carbonyl pyrrole carboxylic acid (ACP). At low temperatures, small cyclic structures are formed. However, at elevated temperatures, a ring–chain transformation leads to the formation of a supramolecular polymer. We demonstrate that this effect is dependent on the

• effect (Figure 7). Most likely, extension of the linker-unit tips the balance between cyclic monomers and the supramolecular polymer. For this reason, no ring–chain transition takes place and no RVT effect could be established. Thus, we focused our investigation on compound 4, which seems to possess the

Supramolecular polymerization of sulfated dendritic peptide amphiphiles into multivalent L-selectin binders

• David Straßburger,
• Svenja Herziger,
• Katharina Huth,
• Moritz Urschbach,
• Rainer Haag and
• Pol Besenius

Beilstein J. Org. Chem. 2021, 17, 97–104, doi:10.3762/bjoc.17.10

• of rigid supramolecular polymers. Since multivalent sulfated supramolecular structures mimic naturally occurring L-selectin ligands, the corresponding affinity was evaluated using a competitive SPR binding assay and benchmarked to an ethylene glycol-decorated supramolecular polymer. Keywords: L

• conditions, supramolecular polymer formation with a length of several hundred nanometers is observed at monomer concentrations as low as 25 µM. Evaluation of the L-selectin binding efficacy The L-selectin binding behavior of the sulfated supramolecular polymer resulting from II was assessed using a

• [26]. These results show that the multivalent presentation of sulfate moieties on the surface of one-dimensional anisotropic supramolecular polymers noticeably enhances their affinity towards surface immobilized L-selectin. However, the binding affinity of the unmodified supramolecular polymer I was

Fabrication, characterization and adsorption properties of cucurbit[7]uril-functionalized polycaprolactone electrospun nanofibrous membranes

• Changzhong Chen,
• Fengbo Liu,
• Xiongzhi Zhang,
• Zhiyong Zhao and
• Simin Liu

Beilstein J. Org. Chem. 2019, 15, 992–999, doi:10.3762/bjoc.15.97

• [20] and supramolecular polymer nanofibers based on pillar[5]arene [21] also were prepared by the electrospinning technique. Cucurbit[n]urils (CB[n]s, n = 5–8, 10) are a family of pumpkin-shaped cyclic host molecules containing a hydrophobic cavity surrounded by two identical hydrophilic portals [22

Synthesis of diamido-bridged bis-pillar[5]arenes and tris-pillar[5]arenes for construction of unique [1]rotaxanes and bis-[1]rotaxanes

• Ying Han,
• Li-Ming Xu,
• Cui-Yun Nie,
• Shuo Jiang,
• Jing Sun and
• Chao-Guo Yan

Beilstein J. Org. Chem. 2018, 14, 1660–1667, doi:10.3762/bjoc.14.142

• feature was obtained in the five single crystals. That is, the longer chain of methyl (ethyl) oxyalkoxybenzoate not only does not inserted in the cavity of the pillar[5]arene to form the pseudo[1]rotaxane, but also does not thread to the cavity of the neighbouring pillar[5]arene to form the supramolecular

• polymer. This result is consistent to the Cao’s previously reported results in the series of pillar[5]arenes bearing aliphatic esters [49], in that they found the chain of methyl oxybutyrate did not threaded into the cavity of pillar[5]arene. The above synthetic pillar[5]arene mono(oxyalkoxy)benzoic acids

Synthesis and supramolecular properties of regioisomers of mononaphthylallyl derivatives of γ-cyclodextrin

• Markéta Bláhová,
• Sergey K. Filippov,
• Lubomír Kováčik,
• Jiří Horský,
• Simona Hybelbauerová,
• Zdenka Syrová,
• Tomáš Křížek and
• Jindřich Jindřich

Beilstein J. Org. Chem. 2017, 13, 2509–2520, doi:10.3762/bjoc.13.248

• supramolecular polymers [9] multifunctional molecules are assembled in a regular manner. To avoid branching, monosubstituted CDs are required for a linear supramolecular polymer of CDs with guest groups attached. Monosubstituted derivatives of CDs [10] include three regioisomers, namely 2I-O-, 3I-O-, and 6I-O

Supramolecular polymer assembly in aqueous solution arising from cyclodextrin host–guest complexation

• Jie Wang,
• Zhiqiang Qiu,
• Yiming Wang,
• Li Li,
• Xuhong Guo,
• Duc-Truc Pham,
• Stephen F. Lincoln and
• Robert K. Prud’homme

Beilstein J. Org. Chem. 2016, 12, 50–72, doi:10.3762/bjoc.12.7

• [112][113][114]. Conclusion and Perspective In this brief review it is shown that there is a plethora of routes to supramolecular polymer networks in aqueous solution based on cyclodextrin host–guest complexation. Through variations in this supramolecular chemistry at the molecular level macroscopic

Synthesis and characterization of a new photoinduced switchable β-cyclodextrin dimer

• Florian Hamon,
• Claire Blaszkiewicz,
• Marie Buchotte,
• Estelle Banaszak-Léonard,
• Hervé Bricout,
• Sébastien Tilloy,
• Eric Monflier,
• Christine Cézard,
• Laurent Bouteiller,
• Christophe Len and
• Florence Djedaini-Pilard

Beilstein J. Org. Chem. 2014, 10, 2874–2885, doi:10.3762/bjoc.10.304

• binding site of the ditopic guest ADAdim 4 and one binding site of a particular β-CD dimer, bearing a terephthalic acid linker, was independent of the number of binding sites, that is, no cooperative effect was observed and a supramolecular polymer was formed. ITC is one of the most interesting methods to

Molecular assembly of amino acid interlinked, topologically symmetric, π-complementary donor–acceptor–donor triads

• M. B. Avinash,
• K. V. Sandeepa and
• T. Govindaraju

Beilstein J. Org. Chem. 2013, 9, 1565–1571, doi:10.3762/bjoc.9.178

• [18], catenane [19], rotaxane [20], self-healable supramolecular polymer [21], aromatic stacking within a coordination cage [22], superamphiphile [23] and thermochromic [24] materials. Notably, Wilson et al. have reported preferential π-stacking of pyrene and NDI amongst a pool of π-electron D-A

Superstructures of fluorescent cyclodextrin via click-reaction

• Arkadius Maciollek,
• Helmut Ritter and
• Rainer Beckert

Beilstein J. Org. Chem. 2013, 9, 827–831, doi:10.3762/bjoc.9.94

• the elongated noncovalent polymeric structures collapse. Keywords: fluorescent dye; cyclodextrins; host–guest interaction; supramolecular polymer; Introduction Most small heterocyclic molecules show low fluorescence. However, as we reported earlier, substituted 4-hydroxythiazoles have a high

• diameter of randomly methylated β-CD, blue: mixture of monomer and oligomer after adding potassium adamantane-1-carboxylate, red: supramolecular polymer of 3. AF4 elution diagram of 3. Synthesis of fluorescent cyclodextrin 3 by click-chemistry.

Azobenzene dye-coupled quadruply hydrogen-bonding modules as colorimetric indicators for supramolecular interactions

• Yagang Zhang and
• Steven C. Zimmerman

Beilstein J. Org. Chem. 2012, 8, 486–495, doi:10.3762/bjoc.8.55

• ][22], modified polymeric materials, functionalized nano-structures [23] and surfaces [24]. Of the numerous supramolecular coupling agents developed those that pair using quadruply hydrogen bonding have arguably received the most attention in the context of supramolecular polymer chemistry. In

Chain stopper engineering for hydrogen bonded supramolecular polymers

• Thomas Pinault,
• Bruno Andrioletti and
• Laurent Bouteiller

Beilstein J. Org. Chem. 2010, 6, 869–875, doi:10.3762/bjoc.6.102

• viscosity of these solutions can be controlled by adding monofunctional compounds, which interact with the chain extremities: chain stoppers. We have synthesized new substituted ureas and thioureas and tested them as chain stoppers for a bis-urea based supramolecular polymer. In particular, the bis-thiourea

• analogue of the bis-urea monomer is shown not to form a supramolecular polymer, but a good chain stopper, because it is a strong hydrogen bond donor and a weak acceptor. Moreover, all substituted ureas tested reduce the viscosity of the supramolecular polymer solutions, but the best chain stopper is

• obtained when two hydrogen bond acceptors are placed in the same relative position as for the monomer and when no hydrogen bond donor is present. Keywords: chain stopper; gel; hydrogen bond; supramolecular polymer; urea; Introduction Supramolecular polymers are linear chains of low molar mass monomers