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Search for "glycoluril" in Full Text gives 14 result(s) in Beilstein Journal of Organic Chemistry.
Acyclic cucurbit[n]uril bearing alkyl sulfate ionic groups
- Christian Akakpo,
- Peter Y. Zavalij and
- Lyle Isaacs
Beilstein J. Org. Chem. 2025, 21, 717–726, doi:10.3762/bjoc.21.55
- are acyclic CB[n]-type receptors which have been extensively studied by our lab and others over the past decade [42][43][44][45][46][47][48][49][50][51][52]. Figure 1 shows the chemical structure of the prototypical acyclic CB[n]-type known as M1 [53][54]. M1 features a central glycoluril tetramer
- modular synthesis, acyclic CB[n] can be easily modified synthetically [42][43][44][45][46][47][61]. Acyclic CB[n]-type receptors featuring different length glycoluril oligomers (monomer–pentamer) and different aromatic walls (e.g., naphthalene, anthracene, triptycene) have been studied [42][62][63][64][65
- to a sulfate group. The synthetic route to C1 starts with the double electrophilic aromatic substitution reaction of methylene-bridged glycoluril tetramer (TetBCE) with W1 in TFA/Ac2O 1:1 which adds the sidewalls and transforms the OH groups into OAc groups to give TetW1OAc in 71% yield as described
Graphical Abstract
Figure 1: Chemical structures of CB[n] and selected acyclic CB[n]-type molecular containers M1 and M0.
Scheme 1: Synthesis of C1. Conditions: a) TFA/Ac2O, 70 °C, 3.5 h, 71%; b) LiOH, 50 °C, 69%; c) dry pyridine, ...
Figure 2: a) 1H NMR spectrum (600, D2O, rt) and b) 13C NMR spectrum recorded (150 MHz, D2O, rt) for C1.
Figure 3: Chemical structures of guests used in this study along with the complexation induced changes in che...
Figure 4: 1H NMR spectra recorded (400 MHz, D2O, rt) for: a) Me6PXDA (0.5 mM), b) a mixture of C1 (0.5 mM) an...
Figure 5: Cross-eyed stereoview of the C1·Me6CHDA complex in the crystal. Color code: C, gray; H, white; N, b...
Figure 6: Cross-eyed stereoview of the crystal packing observed in the molecular cell of C1·Me6CHDA. H-atoms ...
Figure 7: a) Representative plot of DP (μcal s−1) versus time from the titration of C1 (0.1 mM) in the ITC ce...
Switchable molecular tweezers: design and applications
- Pablo Msellem,
- Maksym Dekthiarenko,
- Nihal Hadj Seyd and
- Guillaume Vives
Beilstein J. Org. Chem. 2024, 20, 504–539, doi:10.3762/bjoc.20.45
Graphical Abstract
Figure 1: Principle of switchable molecular tweezers.
Figure 2: Principle of pH-switchable molecular tweezers 1 [19].
Figure 3: a) pH-Switchable tweezers 2 substituted with alkyl chains as switchable lipids. b) Schematic depict...
Figure 4: Modification of spectral properties of 3 by controlled induction of Pt–Pt interactions.
Figure 5: Conformational switching of di(hydroxyphenyl)pyrimidine-based tweezer 4 upon alkylation or fluoride...
Figure 6: Hydrazone-based pH-responsive tweezers 5 for mesogenic modulation.
Figure 7: pH-Switchable molecular tweezers 6 bearing acridinium moieties.
Figure 8: a) Terpyridine and pyridine-hydrazone-pyridine analogs molecular tweezers and b) extended pyridine ...
Figure 9: Terpyridine-based molecular tweezers with M–salphen arms and their field of application. Figure 9 was adapt...
Figure 10: a) Terpyridine-based molecular tweezers for diphosphate recognition [48]; b) bishelicene chiroptical te...
Figure 11: Terpyridine-based molecular tweezers with allosteric cooperative binding.
Figure 12: Terpyridine-based molecular tweezers presenting closed by default conformation.
Figure 13: Pyridine-pyrimidine-pyridine-based molecular tweezers.
Figure 14: Coordination-responsive molecular tweezers based on nitrogen-containing ligands.
Figure 15: Molecular tweezers exploiting the remote bipyridine or pyridine binding to trigger the conformation...
Figure 16: Bipyridine-based molecular tweezers exploiting the direct s-trans to s-cis-switching for a) anion b...
Figure 17: a) Podand-based molecular tweezers [66,67]. b) Application of tweezers 32 for the catalytic allosteric reg...
Figure 18: Anion-triggered molecular tweezers based on calix[4]pyrrole.
Figure 19: Anion-triggered molecular tweezers.
Figure 20: a) Principle of the weak link approach (WLA) developed by Mirkin and its application to b) symmetri...
Figure 21: Molecular tweezers as allosteric catalyst in asymmetric epoxide opening [80].
Figure 22: Allosteric regulation of catalytic activity in ring-opening polymerization with double tweezers 41.
Figure 23: a) Conformational switching of 42 by intramolecular –S–S– bridge formation. b) Shift of conformatio...
Figure 24: a) Redox-active glycoluril-TTF tweezers 44. b) Mechanism of stepwise oxidation of said tweezers wit...
Figure 25: Mechanism of formation of the mixed-valence dimers of tweezers 45.
Figure 26: Mechanism of carbohydrate liberation upon redox-mediated conformation switching of 46.
Figure 27: a) The encapsulation properties of 47 as well as the DCTNF release process from its host–guest comp...
Figure 28: Redox-active bipyridinium-based tweezers. a) With a ferrocenyl hinge 49, b) with a propyl hinge 50 ...
Figure 29: Redox-active calix[4]arene porphyrin molecular tweezers.
Figure 30: a) Mechanism of the three orthogonal stimuli. b) Cubic scheme showing the eight different states of ...
Figure 31: Redox-controlled molecular gripper based on a diquinone resorcin[4]arene.
Figure 32: a) Shinkai's butterfly tweezers and their different host–guest properties depending on the isomer. ...
Figure 33: Cyclam-tethered tweezers and their different host–guest complexes depending on their configuration.
Figure 34: Azobenzene-based catalytic tweezers.
Figure 35: Photoswitchable PIEZO channel mimic.
Figure 36: Stilbene-based porphyrin tweezers for fullerene recognition.
Figure 37: Stiff-stilbene-based tweezers with urea or thiourea functional units for a) anion binding, b) anion...
Figure 38: Feringa’s photoswitchable organocatalyst (a) and different catalyzed reactions with that system (b)....
Figure 39: a) Irie and Takeshita’s thioindigo-based molecular tweezers. b) Family of hemithioindigo-based mole...
Figure 40: Dithienylethylene crown ether-bearing molecular tweezers reported by Irie and co-workers.
Study on the interactions between melamine-cored Schiff bases with cucurbit[n]urils of different sizes and its application in detecting silver ions
- Jun-Xian Gou,
- Yang Luo,
- Xi-Nan Yang,
- Wei Zhang,
- Ji-Hong Lu,
- Zhu Tao and
- Xin Xiao
Beilstein J. Org. Chem. 2021, 17, 2950–2958, doi:10.3762/bjoc.17.204
- , are formed by polymerization of glycoluril, which contains rigid cavities for the study of host–guest chemistry and carbonyl groups for the study of coordination chemistry [16][17][18][19][20]. For the special methyl cucurbit[n]urils with abundant methyl groups, its high density of the
Graphical Abstract
Scheme 1: The Structures of Q[7], Q[8], TMeQ[6], and TBT.
Figure 1: The 1H NMR titration of TBT (1 mM) with an increasing amount of TMeQ[6] from 0 (i), 0.1 (ii), 0.2 (...
Figure 2: The 1H NMR titration of TBT (1 mM) with an increasing amount of Q[7] from 0 (i), 0.1 (ii), 0.5 (iii...
Figure 3: The UV–vis spectra (a) of TBT (20 μM) with an increasing amount of Q[7] from 0.0 to 4.0 equiv; the ...
Figure 4: The UV–vis spectra (a) of TBT (20 μM) with an increasing amount of Q[8] from 0.0 to 4.0 equiv and t...
Figure 5: The UV–vis spectra (a) of Q[7]-TBT (3:1, 20 μM) affected by Mn+ (50 equivalents); histogram of (b) ...
Figure 6: The UV–vis spectra (a) of Q[7]-TBT (20 μM) with an increasing amount of Ag+ from 0.0 to 2.0 equiv; ...
Scheme 2: The synthesis of TBT.
Synthesis of a novel aminobenzene-containing hemicucurbituril and its fluorescence spectral properties with ions
- Qingkai Zeng,
- Qiumeng Long,
- Jihong Lu,
- Li Wang,
- Yuting You,
- Xiaoting Yuan,
- Qianjun Zhang,
- Qingmei Ge,
- Hang Cong and
- Mao Liu
Beilstein J. Org. Chem. 2021, 17, 2840–2847, doi:10.3762/bjoc.17.195
- . Šindelář and Lizal [36] also presented the synthesis of hybrid macrocycles containing glycoluril and aromatic units. In 2014, Keinan et al. [37] reported a series of macrocycles, consisting of alternating urea or thiourea and phenol units, namely, multifarenes. Hitherto, multifarenes and their derivatives
Graphical Abstract
Scheme 1: The evolution of hemicucurbituril analogs.
Scheme 2: The route for the synthesis of aminobenzene-containing hemicucurbituril 4.
Figure 1: The X-ray structure of nitrobenzene-containing hemicucurbituril 9 (CCDC 2094879).
Figure 2: Fluorescence emission spectra (λmax = 349 nm) of 4 (2.5 × 10−5 M) in the presence of 10 equivalents...
Figure 3: Column diagram of fluorescence quenching efficiency of 4 (2.5 × 10−5 M) in the presence of 10 equiv...
Figure 4: Fluorescence emission spectra (λmax = 349 nm) of 4 (2.5 × 10−5 M) in the presence of Fe3+ and Cu2+ ...
Figure 5: Fluorescence emission spectra (λmax = 349 nm) of 4 (2.5 × 10−5 M) in the presence of 20 equivalents...
Figure 6: Column diagram of fluorescence enhancement efficiency of 4 (2.5 × 10−5 M) in the presence of 20 equ...
Insight into functionalized-macrocycles-guided supramolecular photocatalysis
- Minzan Zuo,
- Krishnasamy Velmurugan,
- Kaiya Wang,
- Xueqi Tian and
- Xiao-Yu Hu
Beilstein J. Org. Chem. 2021, 17, 139–155, doi:10.3762/bjoc.17.15
- of electron–hole pairs. Consequently, a high activity of TiO2 could be achieved, and the decolorization of methyl orange was realized efficiently. Cucurbituril-based photocatalysis CBs are a type of macrocyclic molecules made of glycoluril linked by methylene bridges. The name is derived from the
Graphical Abstract
Figure 1: Chemical structures of representative macrocycles.
Figure 2: Ba2+-induced intermolecular [2 + 2]-photocycloaddition of crown ether-functionalized substrates 1 a...
Figure 3: Energy transfer system constructed of a BODIPY–zinc porphyrin–crown ether triad assembly bound to a...
Figure 4: The sensitizer 5 was prepared by a flavin–zinc(II)–cyclen complex for the photooxidation of benzyl ...
Figure 5: Enantiodifferentiating Z–E photoisomerization of cyclooctene sensitized by a chiral sensitizer as t...
Figure 6: Structures of the modified CDs as chiral sensitizing hosts. Adapted with permission from [24], Copyrigh...
Figure 7: Supramolecular 1:1 and 2:2 complexations of AC with the cationic β-CD derivatives 16–21 and subsequ...
Figure 8: Construction of the TiO2–AuNCs@β-CD photocatalyst. Republished with permission of The Royal Society...
Figure 9: Visible-light-driven conversion of benzyl alcohol to H2 and a vicinal diol or to H2 and benzaldehyd...
Figure 10: (a) Structures of CDs, (b) CoPyS, and (c) EY. Republished with permission of The Royal Society of C...
Figure 11: Conversion of CO2 to CO by ReP/HO-TPA–TiO2. Republished with permission of The Royal Society of Che...
Figure 12: Thiacalix[4]arene-protected TiO2 clusters for H2 evolution. Reprinted with permission from [37], Copyri...
Figure 13: 4-Methoxycalix[7]arene film-based TiO2 photocatalytic system. Reprinted from [38], Materials Today Chem...
Figure 14: (a) Photodimerization of 6-methylcoumarin (22). (b) Catalytic cycle for the photodimerization of 22...
Figure 15: Formation of a supramolecular PDI–CB[7] complex and structures of monomers and the chain transfer a...
Figure 16: Ternary self-assembled system for photocatalytic H2 evolution (a) and structure of 27 (b). Figure 16 reprodu...
Figure 17: Structures of COP-1, CMP-1, and their substrate S-1 and S-2.
Figure 18: Supramolecular self-assembly of the light-harvesting system formed by WP5, β-CAR, and Chl-b. Reprod...
Figure 19: Photocyclodimerization of AC based on WP5 and WP6.
Host–guest interaction of cucurbit[8]uril with oroxin A and its effect on the properties of oroxin A
- Zhishu Zeng,
- Jun Xie,
- Guangyan Luo,
- Zhu Tao and
- Qianjun Zhang
Beilstein J. Org. Chem. 2020, 16, 2332–2337, doi:10.3762/bjoc.16.194
- the inclusion compound with Q[8]. Keywords: cucurbit[8]uril; host–guest interaction; inclusion complex; oroxin A; properties; Introduction Cucurbit[n]urils (Q[n]s) are a family of macrocyclic cage compounds synthesized by the condensation of glycoluril and formaldehyde in a strong acidic solution [1
Graphical Abstract
Figure 1: The molecular structure of OA (A) and Q[8] (B).
Figure 2: 1H NMR titration of OA with Q[8] were performed in D2O containing 10% DMSO by volume, OA (500 μmol·L...
Figure 3: (A) The UV–vis absorption spectra recorded for OA in the presence of Q[8] (c(Q[8]), labeled a–k: 0,...
Figure 4: IR spectra recorded for (a) Q[8], (b) OA, (c) a physical mixture of Q[8] and OA, and (d) the OA@Q[8...
Figure 5: The possible interaction mode for OA@Q[8].
Figure 6: The phase-solubility graph obtained for OA in a Q[8] aqueous solution at λ = 275 nm.
Figure 7: The clearance rate curve of ABTS+• upon increasing the concentration of OA and the OA@Q[8] inclusio...
Figure 8: The release curves of OA and OA@Q[8].
Bambusuril analogs based on alternating glycoluril and xylylene units
- Tomáš Lízal and
- Vladimír Šindelář
Beilstein J. Org. Chem. 2019, 15, 1268–1274, doi:10.3762/bjoc.15.124
- Tomas Lizal Vladimir Sindelar Department of Chemistry and RECETOX, Masaryk University, Kamenice 5, 625 00 Brno, Czech Republic 10.3762/bjoc.15.124 Abstract The glycoluril monomer is a popular building block in supramolecular chemistry as it is used for the synthesis of versatile host molecules
- which can interact with cationic, anionic or neutral guest molecules. Here we present the design and synthesis of a new hybrid macrocycle containing glycoluril and aromatic units. The reaction afforded a mixture of macrocyclic homologues from which a two-membered macrocycle was isolated as the main
- [9] and hemicucurbiturils [10]. Bambus[6]urils are a special case of hemicucurbiturils, which comprise six glycoluril units connected by six methylene bridges within their structure [11][12]. Due to their hydrophobic cavity with 12 methine hydrogen atoms available for hydrogen bonding, bambus[6]urils
Graphical Abstract
Scheme 1: Reaction of 2,4-dimethylglycoluril and m-xylylene dibromide.
Figure 1: Molecular structures of 1a and 1b.
Figure 2: Conformers of macrocycles 1a, 1b optimized at the CAM-B3LYP/6-31G(d) level of theory.
Figure 3: 1H NMR spectrum of 1a in MeCN-d3 measured at −40 °C. #Signal of water. *Signal of acetonitrile.
Figure 4: 2D EXSY spectra (ROESY cross-peaks in blue, EXSY cross-peaks in red) measured in MeCN-d3 at −40 °C....
Figure 5: X-ray crystal structure of 1b-1 (left), layered structure of crystal packing (right).
Tetrathiafulvalene – a redox-switchable building block to control motion in mechanically interlocked molecules
- Hendrik V. Schröder and
- Christoph A. Schalley
Beilstein J. Org. Chem. 2018, 14, 2163–2185, doi:10.3762/bjoc.14.190
- host molecule cucurbit[8]uril (9), which is enlarged by an additional glycoluril unit in comparison to 7, provides sufficient space to accommodate two planar molecules with cofacial orientation [68]. When the water-soluble TTF derivative 10 gets oxidized to its radical cation 10●+, a 2:1 complex is
Graphical Abstract
Figure 1: The two one-electron oxidation reactions of tetrathiafulvalene (TTF, 1) and the corresponding prope...
Figure 2: UV–vis spectra and photographs of TTF 2 in its three stable oxidation states (black line = 2, orang...
Figure 3: Structure and conformations of two TTF dimers in solution, the mixed-valence and the radical-cation...
Figure 4: (a) The isomerism problem of TTF. (b)–(d) Major synthetic breakthroughs for the construction of TTF...
Figure 5: (a) Host–guest equilibrium between π-electron-poor cyclophane 3 and different TTFs with their corre...
Figure 6: TTF complexes with different host molecules.
Figure 7: Stable TTF (a) radical-cation and (b) mixed-valence dimers in confined molecular spaces.
Figure 8: A “three-pole supramolecular switch”: Controlled by its oxidation state, TTF (1) jumps back and for...
Figure 9: Redox-controlled closing and opening motion of the artificial molecular lasso 12.
Figure 10: Graphical illustration how a non-degenerate TTF-based shuttle works under electrochemical operation....
Figure 11: The first TTF-based rotaxane 13.
Figure 12: A redox-switchable bistable molecular shuttle 14.
Figure 13: The redox-switchable cyclodextrin-based rotaxane 15.
Figure 14: The redox-switchable non-ionic rotaxane 16 with a pyromellitic diimide macrocycle.
Figure 15: The redox-switchable TTF rotaxane 17 based on a crown/ammonium binding motif.
Figure 16: Structure and operation of the electro- and photochemically switchable rotaxane 18 which acts as po...
Figure 17: (a) The redox-switchable rotaxane 19 with a donor–acceptor pair which is stable in five different s...
Figure 18: Schematic representation of a molecular electronic memory based on a bistable TTF-based rotaxane. (...
Figure 19: Schematic representation of bending motion of a microcantilever beam with gold surface induced by o...
Figure 20: TTF-dimer interactions in a redox-switchable tripodal [4]rotaxane 22.
Figure 21: (a) A molecular friction clutch 23 which can be operated by electrochemical stimuli. (b) Schematic ...
Figure 22: Fusion between rotaxane and catenane: a [3]rotacatenane 24 which can stabilize TTF dimers.
Figure 23: The first TTF-based catenane 25.
Figure 24: Electrochemically controlled circumrotation of the bistable catenane 26.
Figure 25: A tristable switch based on the redox-active [2]catenane 27 with three different stations.
Figure 26: Structure of catenane-functionalized MOF NU-1000 [108] with structural representation of subcomponents. ...
Figure 27: (a) [3]Catenanes 29 and 30 which can stabilize mixed-valence or radical-cation dimers of TTF. (b) S...
Complexation of molecular clips containing fragments of diphenylglycoluril and benzocrown ethers with paraquat and its derivatives
- Leonid S. Kikot',
- Catherine Yu. Kulygina,
- Alexander Yu. Lyapunov,
- Svetlana V. Shishkina,
- Roman I. Zubatyuk,
- Tatiana Yu. Bogaschenko and
- Tatiana I. Kirichenko
Beilstein J. Org. Chem. 2017, 13, 2056–2067, doi:10.3762/bjoc.13.203
- centers, similar to the operating principle of mechanical clips. The most promising for the interaction with paraquat derivatives are molecular tweezers and clips containing fragments of crown ethers, although such examples are not numerous. Nolte et al. showed that the introduction of a glycoluril moiety
- paraquat, the following moieties may be involved: the glycoluril fragment (hydrogen bonds involving the oxygen atoms of the carbonyl groups), the catechol part of the crown ether fragments (π–π stacking interactions) and the polyether chains of benzocrown ethers (C–H···О interactions). The first two
- subunits are identical for all molecular clips. The number of polyether links varies with alteration of the crown ether ring size. To assess the contributions of the glycoluril fragment and the aromatic side walls to the complex stabilities of molecular clips with paraquat we have determined the
Graphical Abstract
Figure 1: Chemical structures of hosts 1–6 and guests 7–10.
Figure 2: HF/6-311+G** calculated 3D molecular electrostatic potential of the guests 7–10. The color code spa...
Figure 3: Partial 1H NMR spectra (300 MHz, CD3CN/CDCl3 4:3, v/v) of (a) free host 3, (b) 3 and 1.0 equiv of 7...
Figure 4: The changes observed in the UV–vis spectra during the titration of clip 2 with paraquat (7) in acet...
Figure 5: Stability constant dependence for the complexes (lgK) of molecular clips 1–5 with guests 7–10 on th...
Figure 6: Molecular structures of complexes of clips 3, 2 and 5 with paraquat (7). Anions and solvate molecul...
Figure 7: Crystal packing of molecules in complexes of clips 2, 3 and 5 with paraquat (7). Anions and solvate...
Figure 8: Molecular structures of complexes 2@8 and 3@8. The hydrogen bonds are shown by blue lines. Anions a...
Figure 9: Molecular structures of complexes 2@9 and 3@9. The hydrogen bonds are represented by blue lines. An...
Figure 10: Molecular structures of complexes 2@10 and 3@10. Anions and solvate molecules are omitted for clari...
Interactions between photoacidic 3-hydroxynaphtho[1,2-b]quinolizinium and cucurbit[7]uril: Influence on acidity in the ground and excited state
- Jonas Becher,
- Daria V. Berdnikova,
- Darinka Dzubiel,
- Heiko Ihmels and
- Phil M. Pithan
Beilstein J. Org. Chem. 2017, 13, 203–212, doi:10.3762/bjoc.13.23
- , cyclodextrins, calixarenes or cucurbiturils, usually has a significant influence on their chemical and physicochemical properties [1][2]. Among the most efficient and versatile host systems along these lines are cucurbit[n]urils (CB[n]) [3][4][5], that consist of methylene-linked glycoluril units that create a
Graphical Abstract
Figure 1: Structures of quinolizinium derivatives 1a–c and 2.
Scheme 1: Synthesis of 3-hydroxynaphtho[1,2-b]quinolizinium bromide (2).
Figure 2: Absorption (A, c = 100 µM) and normalized emission spectra (B, c = 10 µM or Abs. = 0.1 at λex) of d...
Figure 3: Photometric (A) and fluorimetric (B) acid–base titration (λex = 380 nm) of naphthoquinolizinium 2 (c...
Figure 4: Absorption spectra of 2 (c = 100 µM) in MeOH (A) and MeCN (B). Black lines: without additive, red: ...
Figure 5: Normalized emission spectra of 2 (c = 10 µM) in MeOH (A, λex = 400 nm) and MeCN (B, λex = 398 nm). ...
Figure 6: Photometric titration of CB[7] (c = 0.45 mM) to 2 (c = 15 µM) in BPE buffer (with 10% v/v DMSO) at ...
Figure 7: Photometric (A) and fluorimetric (B) acid–base titration (λex = 380 nm) of 2 (c = 15 µM) in the pre...
Scheme 2: Acid–base equilibrium of hydroxynaphthoquinolizinium 2.
Figure 8: Structures of quinolizinium derivatives 6–8.
A journey in bioinspired supramolecular chemistry: from molecular tweezers to small molecules that target myotonic dystrophy
- Steven C. Zimmerman
Beilstein J. Org. Chem. 2016, 12, 125–138, doi:10.3762/bjoc.12.14
- [26]. The now familiar glycoluril motif of 16 clearly has the rigid C-shaped required, and a subsequent report showed it to be capable of complexing dihydroxybenzenes using a combination of aromatic stacking and hydrogen bonding to the urea carbonyl groups [27]. The aromatic stacking surface can be
- a wide range of molecular and supramolecular architectures derived from the simple glycoluril motif [28]. Another early molecular tweezer developed by Harmata was notable because of its chirality. Harmata and his undergraduate student, Tom Murray (who later obtained his Ph.D. in my group), showed
Graphical Abstract
Figure 1: Photographs of Howard E. Zimmerman (July 5, 1926–February 12, 2012) (left) and Jane Zimmerman (née ...
Figure 2: (a) Schematic double helix fully saturated with intercalator (in purple) according to the neighbor ...
Figure 3: Bismethidium molecular tweezer 3 proposed as a graduate student at Columbia University, which was q...
Figure 4: Adenine 8 recognition by carboxylic acid containing tweezer 9 and a component analysis showing “com...
Figure 5: The first determination of the cost of freezing single bond rotations in a host–guest complex.
Figure 6: Glycouril-based molecular clip 16 and 17 developed by Nolte, an example of Harmata’s chiral Kagan-e...
Figure 7: Macrocyclic diacridines and dinaphthalene and the intercalation complexes they may form with one ch...
Figure 8: (a) Hairpin structure of CUGexp seen in (CUG)12. (b) U–U or T–T mismatches with no inter-strand hyd...
Figure 9: (a) CTG trinucleotide repeat expansion in DMPK gene produces expanded transcripts, one which CUGexp...
Glycoluril–tetrathiafulvalene molecular clips: on the influence of electronic and spatial properties for binding neutral accepting guests
- Yoann Cotelle,
- Marie Hardouin-Lerouge,
- Stéphanie Legoupy,
- Olivier Alévêque,
- Eric Levillain and
- Piétrick Hudhomme
Beilstein J. Org. Chem. 2015, 11, 1023–1036, doi:10.3762/bjoc.11.115
- Yoann Cotelle Marie Hardouin-Lerouge Stephanie Legoupy Olivier Aleveque Eric Levillain Pietrick Hudhomme Université d'Angers, Laboratoire MOLTECH-Anjou, CNRS UMR 6200, 2 Boulevard Lavoisier, F-49045 Angers, France 10.3762/bjoc.11.115 Abstract Glycoluril-based molecular clips incorporating
- control binding interaction towards a strong electron acceptor such as tetrafluorotetracyanoquinodimethane (F4-TCNQ) or a weaker electron acceptor such as 1,3-dinitrobenzene (m-DNB). Keywords: donor–acceptor interactions; glycoluril; molecular clips; supramolecular chemistry; tetrathiafulvalene
- , glycoluril-based molecular clips have shown that they were capable of acting as excellent receptors by exploiting the distance between the two aromatic sidewalls which is usually close to 7 Å. Since then, a large number of host systems based on this principle have been synthesized in order to use them for
Graphical Abstract
Figure 1: Structures of molecular clips 1–4.
Scheme 1: Different routes developed for the synthesis of molecular clips 1–4.
Scheme 2: Reaction between diphenylglycoluril with 4,5-bis(bromomethyl)-2-thioxo-1,3-dithiole.
Figure 2: Intramolecular distances between TTF moieties from X-ray analysis for clips 2 and 3 and theoretical...
Figure 3: Cyclic voltammograms of molecular clips 1, 2, 3, 4 and F4-TCNQ at 10−3 M in 0.1 M TBAPF6/CH2Cl2/CH3...
Figure 4: Cyclic voltammograms of molecular clip 2 at different concentrations (left: 10−5 M; middle: 10−4 M;...
Scheme 3: Graphical representation of the stepwise oxidation of molecular clips 1, 2 and 3.
Scheme 4: Electrochemical mechanism used to simulate the CVs of molecular clips 1, 2 and 3.
Figure 5: Chemical oxidation of molecular clip 1 (10−4 M, CH2Cl2) using aliquots of NOSbF6 oxidizing reagent ...
Figure 6: Spectroelectrochemical experiment of molecular clip 1 during the first oxidation step at different ...
Figure 7: Molecular structure of molecular clip 15 and representation of its stepwise oxidation processes pro...
Figure 8: Molecular packing diagram of clips 2 (left) and 3 (right) obtained from X-ray analysis. A molecule ...
Figure 9: Left: Job plot analysis for DNB vs molecular clip 3 ([3 + DNB] = 10−3 M in o-C6H4Cl2 at 800 nm) at ...
Figure 10: UV–visible absorption spectra of F4-TCNQ (CH2Cl2, 10−5 M) upon titration with molecular clip 3 (CH2...
Figure 11: Redox interaction (left) and complexation (right) of F4-TCNQ with molecular clips 3 and 4.
Molecular recognition of organic ammonium ions in solution using synthetic receptors
- Andreas Späth and
- Burkhard König
Beilstein J. Org. Chem. 2010, 6, No. 32, doi:10.3762/bjoc.6.32
Graphical Abstract
Figure 1: Biologically important amines and quaternary ammonium salts: histamine (1), dopamine (2) and acetyl...
Figure 2: Crown ether 18-crown-6.
Figure 3: Conformations of 18-crown-6 (4) in solvents of different polarity.
Figure 4: Binding topologies of the ammonium ion depending on the crown ring size.
Figure 5: A “pseudorotaxane” structure consisting of 24-crown-8 and a secondary ammonium ion (5); R = Ph.
Figure 6: Typical examples of azacrown ethers, cryptands and related aza macrocycles.
Figure 7: Binding of ammonium to azacrown ethers and cryptands [111-113].
Figure 8: A 19-crown-6-ether with decalino blocking groups (11) and a thiazole-dibenzo-18-crown-6-ether (12).
Figure 9: 1,3-Bis(6-oxopyridazin-1-yl)propane derivatives 13 and 14 by Campayo et al.
Figure 10: Fluorescent azacrown-PET-sensors based on coumarin.
Figure 11: Two different pyridino-cryptands (17 and 18) compared to a pyridino-crown (19); chiral ammonium ion...
Figure 12: Pyridino-18-crown-6 ligand (21), a similar acridino-18-crown-6 ligand (22) and a structurally relat...
Figure 13: Ciral pyridine-azacrown ether receptors 24.
Figure 14: Chiral 15-crown-5 receptors 26 and an analogue 18-crown-6 ligand 27 derived from amino alcohols.
Figure 15: C2-symmetric chiral 18-crown-6 amino alcohol derivatives 28 and related macrocycles.
Figure 16: Macrocycles with diamide-diester groups (30).
Figure 17: C2-symmetric chiral aza-18-crown-6 ethers (31) with phenethylamine residues.
Figure 18: Chiral C-pivot p-methoxy-phenoxy-lariat ethers.
Figure 19: Chiral lariat crown ether 34.
Figure 20: Sucrose-based chiral crown ether receptors 36.
Figure 21: Permethylated fructooligosaccharide 37 showing induced-fit chiral recognition.
Figure 22: Biphenanthryl-18-crown-6 derivative 38.
Figure 23: Chiral lariat crown ethers derived from binol by Fuji et al.
Figure 24: Chiral phenolic crown ether 41 with “aryl chiral barriers” and guest amines.
Figure 25: Chiral bis-crown receptor 43 with a meso-ternaphthalene backbone.
Figure 26: Chromogenic pH-dependent bis-crown chemosensor 44 for diamines.
Figure 27: Triamine guests for binding to receptor 44.
Figure 28: Chiral bis-crown phenolphthalein chemosensors 46.
Figure 29: Crown ether amino acid 47.
Figure 30: Luminescent receptor 48 for bis-alkylammonium guests.
Figure 31: Luminescent CEAA (49a), a bis-CEAA receptor for amino acids (49b) and the structure of lysine bindi...
Figure 32: Luminescent CEAA tripeptide for binding small peptides.
Figure 33: Bis crown ether 51a self assembles co-operatively with C60-ammonium ion 51b.
Figure 34: Triptycene-based macrotricyclic dibenzo-[24]-crown-8 ether host 52 and guests.
Figure 35: Copper imido diacetic acid azacrown receptor 53a and the suggested His-Lys binding motif; a copper ...
Figure 36: Urea (54) and thiourea (55) benzo crown receptor for transport and extraction of amino acids.
Figure 37: Crown pyryliums ion receptors 56 for amino acids.
Figure 38: Ditopic sulfonamide bridged crown ether receptor 57.
Figure 39: Luminescent peptide receptor 58.
Figure 40: Luminescent receptor 59 for the detection of D-glucosamine hydrochloride in water/ethanol and lumin...
Figure 41: Guanidinium azacrown receptor 61 for simple amino acids and ditopic receptor 62 with crown ether an...
Figure 42: Chiral bicyclic guanidinium azacrown receptor 63 and similar receptor 64 for the enantioselective t...
Figure 43: Receptors for zwitterionic species based on luminescent CEAAs.
Figure 44: 1,10-Azacrown ethers with sugar podand arms and the anticancer agent busulfan.
Figure 45: Benzo-18-crown-6 modified β-cyclodextrin 69 and β-cyclodextrin functionalized with diaza-18-crown-6...
Figure 46: Receptors for colorimetric detection of primary and secondary ammonium ions.
Figure 47: Porphyrine-crown-receptors 72.
Figure 48: Porphyrin-crown ether conjugate 73 and fullerene-ammonium ion guest 74.
Figure 49: Calix[4]arene (75a), homooxocalix[4]arene (75b) and resorcin[4]arene (75c) compared (R = H, alkyl c...
Figure 50: Calix[4]arene and ammonium ion guest (R = H, alkyl, OAcyl etc.), possible binding sites; A: co-ordi...
Figure 51: Typical guests for studies with calixarenes and related molecules.
Figure 52: Lower rim modified p-tert-butylcalix[5]arenes 82.
Figure 53: The first example of a water soluble calixarene.
Figure 54: Sulfonated water soluble calix[n]arenes that bind ammonium ions.
Figure 55: Displacement assay for acetylcholine (3) with a sulfonato-calix[6]arene (84b).
Figure 56: Amino acid inclusion in p-sulfonatocalix[4]arene (84a).
Figure 57: Calixarene receptor family 86 with upper and lower rim functionalization.
Figure 58: Calix[6]arenes 87 with one carboxylic acid functionality.
Figure 59: Sulfonated calix[n]arenes with mono-substitution at the lower rim systematically studied on their r...
Figure 60: Cyclotetrachromotropylene host (91) and its binding to lysine (81c).
Figure 61: Calixarenes 92 and 93 with phosphonic acids groups.
Figure 62: Calix[4]arene tetraphosphonic acid (94a) and a double bridged analogue (94b).
Figure 63: Calix[4]arene tetraphosphonic acid ester (92c) for surface recognition experiments.
Figure 64: Calixarene receptors 95 with α-aminophosphonate groups.
Figure 65: A bridged homocalix[3]arene 95 and a distally bridged homocalix[4]crown 96.
Figure 66: Homocalix[3]arene ammonium ion receptor 97a and the Reichardt’s dye (97b) for colorimetric assays.
Figure 67: Chromogenic diazo-bridged calix[4]arene 98.
Figure 68: Calixarene receptor 99 by Huang et al.
Figure 69: Calixarenes 100 reported by Parisi et al.
Figure 70: Guest molecules for inclusion in calixarenes 100: DAP × 2 HCl (101a), APA (101b) and Lys-OMe × 2 HC...
Figure 71: Different N-linked peptido-calixarenes open and with glycol chain bridges.
Figure 72: (S)-1,1′-Bi-2-naphthol calixarene derivative 104 published by Kubo et al.
Figure 73: A chiral ammonium-ion receptor 105 based on the calix[4]arene skeleton.
Figure 74: R-/S-phenylalaninol functionalized calix[6]arenes 106a and 106b.
Figure 75: Capped homocalix[3]arene ammonium ion receptor 107.
Figure 76: Two C3 symmetric capped calix[6]arenes 108 and 109.
Figure 77: Phosphorous-containing rigidified calix[6]arene 110.
Figure 78: Calix[6]azacryptand 111.
Figure 79: Further substituted calix[6]azacryptands 112.
Figure 80: Resorcin[4]arene (75c) and the cavitands (113).
Figure 81: Tetrasulfonatomethylcalix[4]resorcinarene (114).
Figure 82: Resorcin[4]arenes (115a/b) and pyrogallo[4]arenes (115c, 116).
Figure 83: Displacement assay for acetylcholine (3) with tetracyanoresorcin[4]arene (117).
Figure 84: Tetramethoxy resorcinarene mono-crown-5 (118).
Figure 85: Components of a resorcinarene based displacement assay for ammonium ions.
Figure 86: Chiral basket resorcin[4]arenas 121.
Figure 87: Resorcinarenes with deeper cavitand structure (122).
Figure 88: Resorcinarene with partially open deeper cavitand structure (123).
Figure 89: Water-stabilized deep cavitands with partially structure (124, 125).
Figure 90: Charged cavitands 126 for tetralkylammonium ions.
Figure 91: Ditopic calix[4]arene receptor 127 capped with glycol chains.
Figure 92: A calix[5]arene dimer for diammonium salt recognition.
Figure 93: Calixarene parts 92c and 129 for the formation molecular capsules.
Figure 94: Encapsulation of a quaternary ammonium cation by two resorcin[4]arene molecules (NMe4+@[75c]2 × Cl−...
Figure 95: Encapsulation of a quaternary ammonium cation by six resorcin[4]arene molecules (NMe3D+@[130]6 × Cl−...
Figure 96: Structure and schematic of cucurbit[6]uril (CB[6], 131a).
Figure 97: Cyclohexanocucurbit[6]uril (CB′[6], 132) and the guest molecule spermine (133).
Figure 98: α,α,δ,δ-Tetramethylcucurbit[6]uril (134).
Figure 99: Structure of the cucurbituril-phthalhydrazide analogue 135.
Figure 100: Organic cavities for the displacement assay for amine differentiation.
Figure 101: Displacement assay methodology for diammonium- and related guests involving cucurbiturils and some ...
Figure 102: Nor-seco-Cucurbituril (±)-bis-ns-CB[6] (140) and guest molecules.
Figure 103: The cucurbit[6]uril based complexes 141 for chiral discrimination.
Figure 104: Cucurbit[7]uril (131c) and its ferrocene guests (142) opposed.
Figure 105: Cucurbit[7]uril (131c) guest inclusion and representative guests.
Figure 106: Cucurbit[7]uril (131c) binding to succinylcholine (145) and different bis-ammonium and bis-phosphon...
Figure 107: Paraquat-cucurbit[8]uril complex 149.
Figure 108: Gluconuril-based ammonium receptors 150.
Figure 109: Examples of clefts (151a), tweezers (151b, 151c, 151d) and clips (151e).
Figure 110: Kemp’s triacid (152a), on example of Rebek’s receptors (152b) and guests.
Figure 111: Amino acid receptor (154) by Rebek et al.
Figure 112: Hexagonal lattice designed hosts by Bell et al.
Figure 113: Bell’s amidinium receptor (156) and the amidinium ion (157).
Figure 114: Aromatic phosphonic acids.
Figure 115: Xylene phosphonates 159 and 160a/b for recognition of amines and amino alcohols.
Figure 116: Bisphosphonate recognition motif 161 for a colorimetric assay with alizarin complexone (163) for ca...
Figure 117: Bisphosphonate/phosphate clip 164 and bisphosphonate cleft 165.
Figure 118: N-Methylpyrazine 166a, N-methylnicotinamide iodide (166b) and NAD+ (166c).
Figure 119: Bisphosphate cavitands.
Figure 120: Bisphosphonate 167 of Schrader and Finocchiaro.
Figure 121: Tweezer 168 for noradrenaline (80b).
Figure 122: Different tripods and heparin (170).
Figure 123: Squaramide based receptors 172.
Figure 124: Cage like NH4+ receptor 173 of Kim et al.
Figure 125: Ammonium receptors 174 of Chin et al.
Figure 126: 2-Oxazolin-based ammonium receptors 175a–d and 176 by Ahn et al.
Figure 127: Racemic guest molecules 177.
Figure 128: Tripods based on a imidazole containing macrocycle (178) and the guest molecules employed in the st...
Figure 129: Ammonium ion receptor 180.
Figure 130: Tetraoxa[3.3.3.3]paracyclophanes 181 and a cyclophanic tetraester (182).
Figure 131: Peptidic bridged paraquat-cyclophane.
Figure 132: Shape-selective noradrenaline host.
Figure 133: Receptor 185 for binding of noradrenaline on surface layers from Schrader et al.
Figure 134: Tetraphosphonate receptor for binding of noradrenaline.
Figure 135: Tetraphosphonate 187 of Schrader and Finocchiaro.
Figure 136: Zinc-Porphyrin ammonium-ion receptors 188 and 189 of Mizutani et al.
Figure 137: Zinc porphyrin receptor 190.
Figure 138: Zinc porphyrin receptors 191 capable of amino acid binding.
Figure 139: Zinc-porphyrins with amino acid side chains for stereoinduction.
Figure 140: Bis-zinc-bis-porphyrin based on Tröger’s base 193.
Figure 141: BINAP-zinc-prophyrin derivative 194 and it’s guests.
Figure 142: Bisaryl-linked-zinc-porphyrin receptors.
Figure 143: Bis-zinc-porphyrin 199 for diamine recognition and guests.
Figure 144: Bis-zinc-porphyrin crown ether 201.
Figure 145: Bis-zinc-porphyrin 202 for stereodiscrimination (L = large substituent; S = small substituent).
Figure 146: Bis-zinc-porphyrin[3]rotaxane and its copper complex and guests.
Figure 147: Dien-bipyridyl ligand 206 for co-ordination of two metal atoms.
Figure 148: The ligand and corresponding tetradentate co-complex 207 serving as enantioselective receptor for a...
Figure 149: Bis(oxazoline)–copper(II) complex 208 for the recognition of amino acids in aqueous solution.
Figure 150: Zinc-salen-complexes 209 for the recognition tertiary amines.
Figure 151: Bis(oxazoline)–copper(II) 211 for the recognition of amino acids in aqueous solution.
Figure 152: Zn(II)-complex of a C2 terpyridine crown ether.
Figure 153: Displacement assay and receptor for aspartate over glutamate.
Figure 154: Chiral complex 214 for a colorimetric displacement assay for amino acids.
Figure 155: Metal complex receptor 215 with tripeptide side arms.
Figure 156: A sandwich complex 216 and its displaceable dye 217.
Figure 157: Lanthanide complexes 218–220 for amino acid recognition.
Figure 158: Nonactin (221), valinomycin (222) and vancomycin (223).
Figure 159: Monesin (224a) and a chiral analogue for enantiodiscrimination of ammonium guests (224b).
Figure 160: Chiral podands (226) compared to pentaglyme-dimethylether (225) and 18-crown-6 (4).
Figure 161: Lasalocid A (228).
Figure 162: Lasalocid derivatives (230) of Sessler et al.
Figure 163: The Coporphyrin I tetraanion (231).
Figure 164: Linear and cyclic peptides for ammonium ion recognition.
Figure 165: Cyclic and bicyclic depsipeptides for ammonium ion recognition.
Figure 166: α-Cyclodextrin (136a) and novocaine (236).
Figure 167: Helical diol receptor 237 by Reetz and Sostmann.
Figure 168: Ammonium binding spherand by Cram et al. (238a) and the cyclic[6]metaphenylacetylene 238b in compar...
Figure 169: Receptor for peptide backbone and ammonium binding (239).
Figure 170: Anion sensor principle with 3-hydroxy-2-naphthanilide of Jiang et al.
Figure 171: 7-bromo-3-hydroxy-N-(2-hydroxyphenyl)naphthalene 2-carboxamide (241) and its amine binding.
Figure 172: Naturally occurring catechins with affinity to quaternary ammonium ions.
Figure 173: Spiropyran (244) and merocyanine form (244a) of the amino acid receptors of Fuji et al.
Figure 174: Coumarin aldehyde (245) and its iminium species with amino acid bound (245a) by Glass et al.
Figure 175: Coumarin aldehyde appended with boronic acid.
Figure 176: Quinolone aldehyde dimers by Glass et al.
Figure 177: Chromogenic ammonium ion receptors with trifluoroacetophenone recognition motifs.
Figure 178: Chromogenic ammonium ion receptor with trifluoroacetophenone recognition motif bound on different m...
Control of stilbene conformation and fluorescence in self-assembled capsules
- Mark R. Ams,
- Dariush Ajami,
- Stephen L. Craig,
- Jye-Shane Yang and
- Julius Rebek Jr
Beilstein J. Org. Chem. 2009, 5, No. 79, doi:10.3762/bjoc.5.79
- with alkyl chain C17H36 was also investigated. No additional fluorescence was observed when C17H36 was a guest (see Supporting Information File 1 for fluorescence and NMR spectra). Earlier we showed that it is possible to reversibly interconvert capsules 1.1 and 1.74.1. The weakly basic glycoluril
- spacer is protonated by addition of gaseous HCl and precipitates in typical organic solutions. The remaining components reassemble to the original capsule 1.1 [11]. Subsequent addition of NEt3 releases the glycoluril into solution and restores the extended capsule 1.74.1. This was shown previously to be
Graphical Abstract
Figure 1: (Top) Tetraimide cavitand 1, the dimeric capsule 1.1 and its cartoon representation. (Bottom) The s...
Figure 2: Room temperature fluorescence spectra at λexc = 318 nm for 10 µM mesitylene solutions of 4,4′-dimet...
Figure 3: (Top) Glycouril 7, the extended capsule 1.74.1, (only one enantiomeric arrangement is shown) and it...
Figure 4: Room temperature emission spectra for 10 µM solutions of 4-ethyl-4′-ethylstilbene (3) in the capsul...
