Investigation of the Amide Linkages on Cooperative Supramolecular Polymerization of Organoplatinum(II) Complexes

Cooperative supramolecular polymerization of π-conjugated compounds into one-dimensional nanostructures has received tremendous attentions in recent years. It is commonly achieved by incorporating amide linkages into the monomeric structures, which provide hydrogen bonds for intermolecular non-covalent complexation. Herein, the effect of amide linkages is elaborately studied, by comparing supramolecular polymerization behaviors of two structurally similar monomers with the same platinum(II) acetylide cores. As compared to the N-phenyl benzamide linkages, N-[(1S)-1-phenylethyl] benzamide linkages give rise to effective chirality transfer behaviors due to the closer distances between the chiral units and the platinum(II) acetylide core. They also provide stronger intermolecular hydrogen bonding strength, which consequently brings higher thermo-stability and enhanced gelation capability for the resulting supramolecular polymers. Supramolecular polymerization is further strengthened by varying the monomers from monotopic to ditopic structures. Hence, with the judicious modulation of structural parameters, the current study opens up new avenues for the rational design of supramolecular polymeric systems.

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Fluorescent supramolecular polymers of barbiturate dyes with thiophene-cored twisted π-systems

Chemical Science ◽

10.1039/d1sc06246h ◽

2022 ◽

Author(s):

Maika Kawaura ◽

Takumi Aizawa ◽

Sho Takahashi ◽

Hiroshi Miyasaka ◽

Hikaru Sotome ◽

...

Keyword(s):

Supramolecular Polymers ◽

Conjugated Molecules ◽

One Dimensional ◽

Emission Efficiency ◽

Supramolecular Polymerization ◽

One Dimensional Nanostructures

Because supramolecular polymerization of emissive p-conjugated molecules depends strongly on p–pstacking interaction, the formation of well-defined one-dimensional nanostructures often results in decrease or only small increase of emission efficiency. This is also true...

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

Beilstein Journal of Organic Chemistry ◽

10.3762/bjoc.17.10 ◽

2021 ◽

Vol 17 ◽

pp. 97-104

Author(s):

David Straßburger ◽

Svenja Herziger ◽

Katharina Huth ◽

Moritz Urschbach ◽

Rainer Haag ◽

...

Keyword(s):

Self Assembly ◽

Supramolecular Polymers ◽

Supramolecular Polymer ◽

Peptide Amphiphile ◽

One Dimensional ◽

Cryogenic Transmission Electron Microscopy ◽

Naturally Occurring ◽

Selectin Ligands ◽

Transmission Electron ◽

Supramolecular Polymerization

The synthesis of a sulfate-modified dendritic peptide amphiphile and its self-assembly into one-dimensional rod-like architectures in aqueous medium is reported. The influence of the ionic strength on the supramolecular polymerization was probed via circular dichroism spectroscopy and cryogenic transmission electron microscopy. Physiological salt concentrations efficiently screen the charges of the dendritic building block equipped with eight sulfate groups and trigger the formation 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.

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Supramolecular Systems Containing B–N Frustrated Lewis Pairs of Tris(pentafluorophenyl)borane and Triphenylamine Derivatives

Organic Materials ◽

10.1055/s-0041-1727235 ◽

2021 ◽

Vol 03 (02) ◽

pp. 174-183

Author(s):

P. Chidchob ◽

S. A. H. Jansen ◽

S. C. J. Meskers ◽

E. Weyandt ◽

N. P. van Leest ◽

...

Keyword(s):

Materials Science ◽

Supramolecular Polymers ◽

Frustrated Lewis Pairs ◽

Paramagnetic Resonance ◽

Donor And Acceptor ◽

Donor Acceptor ◽

Noncovalent Polymers ◽

Electron Paramagnetic ◽

Supramolecular Polymerization ◽

Lewis Pairs

The introduction of a chemical additive to supramolecular polymers holds high potential in the development of new structures and functions. In this regard, various donor- and acceptor-based molecules have been applied in the design of these noncovalent polymers. However, the incorporation of boron–nitrogen frustrated Lewis pairs in such architectures is still rare despite their many intriguing properties in catalysis and materials science. The limited choices of suitable boron derivatives represent one of the main limitations for the advancement in this direction. Here, we examine the use of the commercially available tris(pentafluorophenyl)borane with various triphenylamine derivatives to create supramolecular B–N charge transfer systems. Our results highlight the importance of a proper balance between the donor/acceptor strength and the driving force for supramolecular polymerization to achieve stable, long-range ordered B–N systems. Detailed analyses using electron paramagnetic resonance and optical spectroscopy suggest that tris(pentafluorophenyl)borane displays complex behavior with the amide-based triphenylamine supramolecular polymers and may interact in dimers or larger chiral aggregates, depending on the specific structure of the triphenylamines.

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Living supramolecular polymerization of fluorinated cyclohexanes

Nature Communications ◽

10.1038/s41467-021-23370-y ◽

2021 ◽

Vol 12 (1) ◽

Author(s):

Oleksandr Shyshov ◽

Shyamkumar Vadakket Haridas ◽

Luca Pesce ◽

Haoyuan Qi ◽

Andrea Gardin ◽

...

Keyword(s):

Dipole Moment ◽

Self Assembly ◽

Materials Science ◽

Helical Structure ◽

The Self ◽

Supramolecular Polymers ◽

Aliphatic Compound ◽

Double Helical Structure ◽

Key Driver ◽

Supramolecular Polymerization

AbstractThe development of powerful methods for living covalent polymerization has been a key driver of progress in organic materials science. While there have been remarkable reports on living supramolecular polymerization recently, the scope of monomers is still narrow and a simple solution to the problem is elusive. Here we report a minimalistic molecular platform for living supramolecular polymerization that is based on the unique structure of all-cis 1,2,3,4,5,6-hexafluorocyclohexane, the most polar aliphatic compound reported to date. We use this large dipole moment (6.2 Debye) not only to thermodynamically drive the self-assembly of supramolecular polymers, but also to generate kinetically trapped monomeric states. Upon addition of well-defined seeds, we observed that the dormant monomers engage in a kinetically controlled supramolecular polymerization. The obtained nanofibers have an unusual double helical structure and their length can be controlled by the ratio between seeds and monomers. The successful preparation of supramolecular block copolymers demonstrates the versatility of the approach.

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Counteranion- and Solvent-Mediated Chirality Transfer in the Supramolecular Polymerization of Luminescent Platinum(II) Complexes

Angewandte Chemie International Edition ◽

10.1002/anie.201811943 ◽

2018 ◽

Vol 57 (52) ◽

pp. 17189-17193 ◽

Cited By ~ 13

Author(s):

Qingyun Wan ◽

Xin-Shan Xiao ◽

Wai-Pong To ◽

Wei Lu ◽

Yong Chen ◽

...

Keyword(s):

Chirality Transfer ◽

Supramolecular Polymerization

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Rational design of cyanide-bridged heterometallic M(I)–Mn(II) (M = Ag, Au) one-dimensional chain complexes: synthesis, crystal structures and magnetic properties

CrystEngComm ◽

10.1039/b903174j ◽

2009 ◽

Vol 11 (11) ◽

pp. 2447 ◽

Cited By ~ 22

Author(s):

Daopeng Zhang ◽

Hailong Wang ◽

Laijin Tian ◽

Jianzhuang Jiang ◽

Zhong-Hai Ni

Keyword(s):

Magnetic Properties ◽

Crystal Structures ◽

Rational Design ◽

Dimensional Chain ◽

One Dimensional ◽

Chain Complexes

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Counteranion- and Solvent-Mediated Chirality Transfer in the Supramolecular Polymerization of Luminescent Platinum(II) Complexes

Angewandte Chemie ◽

10.1002/ange.201811943 ◽

2018 ◽

Vol 130 (52) ◽

pp. 17435-17439 ◽

Cited By ~ 2

Author(s):

Qingyun Wan ◽

Xin-Shan Xiao ◽

Wai-Pong To ◽

Wei Lu ◽

Yong Chen ◽

...

Keyword(s):

Chirality Transfer ◽

Supramolecular Polymerization

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Lipophilicity and Click Reactivity Determine the Performance of Bioorthogonal Tetrazine Tools in Pretargeted in Vivo Chemistry

10.26434/chemrxiv.13482594 ◽

2020 ◽

Author(s):

Johanna Stéen ◽

Jesper Tranekjær Jørgensen ◽

Denk Christoph ◽

Umberto Maria Battisti ◽

Kamilla Nørregaard ◽

...

Keyword(s):

Targeted Delivery ◽

Rational Design ◽

Structural Parameters ◽

Early Time ◽

High Rate ◽

Drug Conjugates ◽

Compound Libraries ◽

Drug Concentrations ◽

The Impact

The development of highly selective and fast biocompatible reactions for ligation and cleavage has paved the way for new diagnostic and therapeutic applications of in vivo chemistry. The concept of bioorthogonal pretargeting has attracted considerable interest, in particular for the targeted delivery of radionuclides and drugs. In nuclear medicine, pretargeting can provide increased target-to-background ratios at early time-points compared to traditional approaches. This reduces the radiation burden to healthy tissue and, depending on the selected radionuclide, enables better imaging contrast or higher therapeutic efficiency. Moreover, bioorthogonally triggered cleavage of pretargeted antibody-drug conjugates represents an emerging strategy to achieve controlled release and locally increased drug concentrations. The toolbox of bioorthogonal reactions has significantly expanded in the past decade, with the tetrazine ligation being the fastest and one of the most versatile in vivo chemistries. Progress in the field, however, relies heavily on the development and evaluation of (radio)labeled compounds, preventing the use of compound libraries for systematic studies. The rational design of tetrazine probes and triggers has thus been impeded by the limited understanding of the impact of structural parameters on the in vivo ligation performance. In this work, we describe the development of a pretargeted blocking assay that allows for the investigation of the in vivo fate of a structurally diverse library of 45 unlabeled tetrazines and their capability to reach and react with pretargeted trans-cyclooctene (TCO)-tagged antibodies in tumor-bearing mice. This study enabled us to assess the correlation of click reactivity and lipophilicity of tetrazines with their in vivo performance. In particular, high rate constants (>50,000 M-1s-1) for the reaction with TCO and low calculated logD7.4 values (below -3) of the tetrazine were identified as strong indicators for successful pretargeted in vivo click chemistry. Click-radiolabeling gave access to a set of selected 18F-labeled tetrazines, including highly reactive scaffolds, which were used in pretargeted PET imaging studies to confirm the results from the blocking study. These insights thus enable the rational design of tetrazine probes for in vivo application and will thereby assist the clinical translation of bioorthogonal pretargeting.

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Controlling the length of porphyrin supramolecular polymers via coupled equilibria and dilution-induced supramolecular polymerization

Nature Communications ◽

10.1038/s41467-021-27831-2 ◽

2022 ◽

Vol 13 (1) ◽

Author(s):

Elisabeth Weyandt ◽

Luigi Leanza ◽

Riccardo Capelli ◽

Giovanni M. Pavan ◽

Ghislaine Vantomme ◽

...

Keyword(s):

Complex Systems ◽

Self Assembly ◽

Chiral Discrimination ◽

Coarse Grained ◽

Supramolecular Polymers ◽

Supramolecular System ◽

Precise Control ◽

Aggregate Morphology ◽

The Individual ◽

Supramolecular Polymerization

AbstractMulti-component systems often display convoluted behavior, pathway complexity and coupled equilibria. In recent years, several ways to control complex systems by manipulating the subtle balances of interaction energies between the individual components have been explored and thereby shifting the equilibrium between different aggregate states. Here we show the enantioselective chain-capping and dilution-induced supramolecular polymerization with a Zn2+-porphyrin-based supramolecular system when going from long, highly cooperative supramolecular polymers to short, disordered aggregates by adding a monotopic Mn3+-porphyrin monomer. When mixing the zinc and manganese centered monomers, the Mn3+-porphyrins act as chain-cappers for Zn2+-porphyrin supramolecular polymers, effectively hindering growth of the copolymer and reducing the length. Upon dilution, the interaction between chain-capper and monomers weakens as the equilibria shift and long supramolecular polymers form again. This dynamic modulation of aggregate morphology and length is achieved through enantioselectivity in the aggregation pathways and concentration-sensitive equilibria. All-atom and coarse-grained molecular simulations provide further insights into the mixing of the species and their exchange dynamics. Our combined experimental and theoretical approach allows for precise control of molecular self-assembly and chiral discrimination in complex systems.

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