Solvent dependent pathway complexity and seeded supramolecular polymerization

2018 ◽  
Vol 54 (45) ◽  
pp. 5720-5723 ◽  
Author(s):  
Goutam Ghosh ◽  
Suhrit Ghosh
Keyword(s):  
Supramolecular Polymer ◽  
Cyclic Hydrocarbon ◽  
Supramolecular Polymerization ◽  
Dependent Pathway

cNDI-1 exhibits an off-pathway aggregate in cyclic hydrocarbon (MCH) but produces a helical supramolecular polymer in linear alkane (decane) by well-defined J-aggregation.

scholarly journals Oriented arrangement of simple monomers enabled by confinement: towards living supramolecular polymerization

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Yingtong Zong ◽  
Si-Min Xu ◽  
Wenying Shi ◽  
Chao Lu
Keyword(s):  
Activation Barrier ◽  
Degree Of Polymerization ◽  
Supramolecular Polymer ◽  
Energy Principle ◽  
Spontaneous Nucleation ◽  
Pyrene Derivatives ◽  
Multifunctional Molecules ◽  
Double Hydroxide ◽  
Supramolecular Polymerization ◽  
Kinetics Of

AbstractThe living supramolecular polymerization technique provides an exciting research avenue. However, in comparison with the thermodynamic spontaneous nucleation, using simple monomers to realize living supramolecular polymerization is hardly possible from an energy principle. This is because the activation barrier of kinetically trapped simple monomer (nucleation step) is insufficiently high to control the kinetics of subsequent elongation. Here, with the benefit of the confinement from the layered double hydroxide (LDH) nanomaterial, various simple monomers, (such as benzene, naphthalene and pyrene derivatives) successfully form living supramolecular polymer (LSP) with length control and narrow dispersity. The degree of polymerization can reach ~6000. Kinetics studies reveal LDH overcomes a huge energy barrier to inhibit undesired spontaneous nucleation of monomers and disassembly of metastable states. The universality of this strategy will usher exploration into other multifunctional molecules and promote the development of functional LSP.

scholarly journals Biomimetic Design of a Robustly Stabilized Folded State Enabling Seed-Initiated Helical Supramolecular Polymerization Under Microfluidic Mixing

2020 ◽  
Author(s):  
Soichiro Ogi ◽  
Aiko Takamatsu ◽  
Kentaro Matsumoto ◽  
Shigehiro Yamaguchi
Keyword(s):  
Molecular Diffusion ◽  
Helical Structure ◽  
Spectroscopic Studies ◽  
Membered Ring ◽  
Racemic Mixture ◽  
Supramolecular Polymer ◽  
Spontaneous Transformation ◽  
Microfluidic Mixing ◽  
Intramolecular Hydrogen ◽  
Supramolecular Polymerization

We have investigated the folding and assembly behavior of an alanine-based monomeric diamide and a cystine-based dimeric diamide bearing pyrene units and solubilizing alkyl chains at their C-termini andN-termini, respectively. In low-polarity solvents, the former molecule forms a folded 7-membered ring conformation with an intramolecular hydrogen bond, while the latter molecule forms a 14-membered ring through double intramolecular hydrogen bonds between two diamide units. Spectroscopic studies revealed that both folded states are thermodynamically unstable and eventually transform into more energetically stable supramolecular polymers. Importantly, compared to the alanine-based diamide, the cystine-based dimeric diamide exhibits a superior kinetic stability in the metastable folded state, as well asan increased thermodynamic stability in the aggregated state. Consequently, spontaneous transformation from the folded state into the aggregated state is retarded even under the conditions of rapid molecular diffusion. Accordingly, the initiation of supramolecular polymerization can be regulated via a seeding approach under microfluidic mixing conditions. Furthermore, the supramolecular polymer composed of the cystine-based dimeric diamide has a helical structure with an enhanced chiral excitonic coupling between the transition dipoles of the pyrene units. Taking advantage of the self-sorting behavior observed in a mixture of l-cysteine- and d-cysteine-based dimeric diamides, a two-step supramolecular polymerization from a racemic mixture was achieved by stepwise addition of the corresponding seeds.

scholarly journals Upper-rim functionalization and supramolecular polymerization of a feet-to-feet-connected biscavitand

2020 ◽  
Vol 56 (26) ◽  
pp. 3733-3736 ◽  
Author(s):  
Daisuke Shimoyama ◽  
Ryo Sekiya ◽  
Takeharu Haino
Keyword(s):  
Solid State ◽  
Good Yield ◽  
Supramolecular Polymer ◽  
Iodination Reaction ◽  
Self Assembled ◽  
Upper Rim ◽  
Supramolecular Polymerization

An octaiodobiscavitand was synthesized via an aromatic Finkelstein iodination reaction in good yield. An octa-functionalized biscavitand self-assembled to form a supramolecular polymer in the solid state.

In situ supramolecular polymerization promoted by the marriage of dynamic covalent bonding and pillar[5]arene-based host–guest interaction

2017 ◽  
Vol 53 (6) ◽  
pp. 1144-1147 ◽  
Author(s):  
Panpan Chen ◽  
Yujuan Zhou ◽  
Jie Yang
Keyword(s):  
Covalent Bonding ◽  
Supramolecular Polymer ◽  
Dual Responsive ◽  
Supramolecular Polymerization

A temperature and pH dual-responsive linear supramolecular polymer was efficiently constructed by unifying dynamic covalent bonding and pillar[5]arene-based host–guest interaction through in situ supramolecular polymerization.

scholarly journals Supramolecular Polymerization with Dynamic Self-Sorting Sequence Control

2019 ◽  
Author(s):  
Shi Xiujuan ◽  
Xiaodong Zhang ◽  
Xin-Long Ni ◽  
Haoke Zhang ◽  
Peifa Wei ◽  
...  
Keyword(s):  
Fluorescence Spectra ◽  
Structural Changes ◽  
Fluorescent Sensor ◽  
Ternary Complexes ◽  
Water Soluble ◽  
Supramolecular Interactions ◽  
Supramolecular Polymers ◽  
Supramolecular Polymer ◽  
Artificial Urine ◽  
Supramolecular Polymerization

Synthetic polymerization and supramolecular polymerization with sequence control is far from an easy task. Herein, a narcissistic self-sorting supramolecular polymer is prepared with a sequence of (−AA−BB−)n by using cucur-bit[8]uril (CB[8])-based ternary complexes as supramolecular monomers, which are spontaneously formed from starting materials of heteroditopic AB-type guest and CB[8]. The process of supramolecular polymerization and their structural changes at each stage of polymerization have been successfully demonstrated by NMR, UV-Vis and fluorescence spectra. The self-sorting starts from the second step of polymerization after the formation of different ternary complexes as supra-monomers. The dynamic supramolecular interactions and the thermodynamic stability of the host–guest complexes are found to be the crucial factors to drive the sequence control of the supramolecular polymers. Furthermore, the water-soluble supramolecular polymer is red-emissive, which can serve as fluorescent sensor to detect morphine in artificial urine with considerable stability, sensitivity and accuracy. And it can also distinguish heroin and morphine, which are two kinds of opioids with similar structures.

Kinetics of Supramolecular Polymerization: MSOA and HG Mechanisms

2006 ◽  
Vol 11-12 ◽  
pp. 639-642
Author(s):  
Yan Li Fan ◽  
Hao Jin ◽  
Xiao Hua Zhi ◽  
Ya Fei Lu
Keyword(s):  
Degree Of Polymerization ◽  
Polymer Chains ◽  
Supramolecular Polymer ◽  
Helical Polymer ◽  
Repeat Units ◽  
Helical Growth ◽  
Step Growth ◽  
Supramolecular Polymerization ◽  
Kinetics Of ◽  
Supramolecular Chains

Multistage open association (MSOA) and helical growth (HG) mechanisms describe the linear growth of supramolecular polymer chains and the helical growth of supramolecular chains with the intra-assemble cooperative effect, respectively. Both mechanisms were proposed by Ciferri. Assuming that supramolecular polymerization follows the step-growth and the interaction between repeat units is independent of molecular weight, the kinetics of MSOA and HG can be mathematically analyzed. In this paper the relationships among degree of polymerization (DP), unimer concentration (C0), and equilibrium constant (K) for MSOA and DP , concentration of helical polymer ( h C ), and nucleation factor (σ ) for HG were derived.

scholarly journals Magnetic Control over the Topology of Supramolecular Rod Networks

2020 ◽  
Author(s):  
Vincent Marichez ◽  
Akihiro Sato ◽  
Peter Dunne ◽  
Jorge Leira-Iglesias ◽  
Georges Formon ◽  
...  
Keyword(s):  
Magnetic Fields ◽  
Single Molecule ◽  
Magnetic Energy ◽  
Advanced Materials ◽  
Supramolecular Polymer ◽  
Demagnetizing Field ◽  
Single Molecule Level ◽  
Field Gradients ◽  
Paramagnetic Ions ◽  
Supramolecular Polymerization

Understanding and controlling supramolecular polymerization are of fundamental importance to create advanced materials and devices. Many stimuli have been explored in the past decades, but magnetic fields and field gradients have received little attention. This is because magnets do not provide enough magnetic energy to overcome thermal noise at the single molecule level. Here we show that significant changes in network topology of Gd<sup>3+</sup>-decorated supramolecular polymer rods can nevertheless be observed using magnetic fields of order 1 T at room temperature. The structure of the rod networks is influenced during a slow diffusive process over a timescale of hours by the anisotropy of the demagnetizing field. Our approach opens opportunities to control and tune structure formation of many supramolecular and coordination polymers using a variety of rare earth or other paramagnetic ions.

Supramolecular Polymerization with Dynamic Self-Sorting Sequence Control

2019 ◽  
Author(s):  
Shi Xiujuan ◽  
Xiaodong Zhang ◽  
Xin-Long Ni ◽  
Haoke Zhang ◽  
Peifa Wei ◽  
...  
Keyword(s):  
Fluorescence Spectra ◽  
Structural Changes ◽  
Fluorescent Sensor ◽  
Ternary Complexes ◽  
Water Soluble ◽  
Supramolecular Interactions ◽  
Supramolecular Polymers ◽  
Supramolecular Polymer ◽  
Artificial Urine ◽  
Supramolecular Polymerization

Synthetic polymerization and supramolecular polymerization with sequence control is far from an easy task. Herein, a narcissistic self-sorting supramolecular polymer is prepared with a sequence of (−AA−BB−)n by using cucur-bit[8]uril (CB[8])-based ternary complexes as supramolecular monomers, which are spontaneously formed from starting materials of heteroditopic AB-type guest and CB[8]. The process of supramolecular polymerization and their structural changes at each stage of polymerization have been successfully demonstrated by NMR, UV-Vis and fluorescence spectra. The self-sorting starts from the second step of polymerization after the formation of different ternary complexes as supra-monomers. The dynamic supramolecular interactions and the thermodynamic stability of the host–guest complexes are found to be the crucial factors to drive the sequence control of the supramolecular polymers. Furthermore, the water-soluble supramolecular polymer is red-emissive, which can serve as fluorescent sensor to detect morphine in artificial urine with considerable stability, sensitivity and accuracy. And it can also distinguish heroin and morphine, which are two kinds of opioids with similar structures.

scholarly journals Binding properties and supramolecular polymerization of a water-soluble resorcin[4]arene

2019 ◽  
Vol 6 (8) ◽  
pp. 1236-1243 ◽  
Author(s):  
Jacobs H. Jordan ◽  
Anthony Wishard ◽  
Joel T. Mague ◽  
Bruce C. Gibb
Keyword(s):  
Water Soluble ◽  
Supramolecular Polymer ◽  
Binding Properties ◽  
Supramolecular Polymerization

A ditopic water-soluble resorcinarene is shown to bind salts and undergo self-inclusion to assembly into a supramolecular polymer.

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

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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