scholarly journals Triple Self-Sorting in Constitutional Dynamic Networks: Parallel Generation of Cu(I), Fe(II) and Zn(II) Imine-Based Metal Complexes

2019 ◽  
Author(s):  
Jean-François Ayme ◽  
Sébastien Dhers ◽  
Jean-Marie Lehn
Keyword(s):  
Metal Complexes ◽  
Driving Forces ◽  
Dynamic Networks ◽  
Dynamic Network ◽  
The Self ◽  
Self Assembling ◽  
Kinetic Trap ◽  
Sorting Process ◽  
Agonistic Relationships ◽  
The Stability

<div>Three imine-based metal complexes, having no overlap in terms of their compositions, have been simultaneously generated from the self-sorting of a constitutional dynamic library (CDL) containing three amines, three aldehydes and three metal salts. The hierarchical ordering of the stability of three metal complexes assembled and the leveraging of the antagonistic and agonistic relationships existing between the constituents within the constitutional dynamic network corresponding to the CDL were pivotal in achieving the desired sorting. The mechanism and the driving forces underlying the self-sorting process have been studied by NMR. The self-sorting of the Fe(II) and Zn(II) complexes was found to depend on an interplay between the thermodynamic driving forces and a kinetic trap involved in their assembling. These results also exemplify the concept of “simplexity” –the fact that the output of a self-assembling system may be simplified by increasing its initial compositional complexity—as the two complexes could self-sort only in the presence of the third pair of organic components, those of the Cu(I) complex.</div><br>

scholarly journals Triple Self-Sorting in Constitutional Dynamic Networks: Parallel Generation of Cu(I), Fe(II) and Zn(II) Imine-Based Metal Complexes

2019 ◽  
Author(s):  
Jean-François Ayme ◽  
Sébastien Dhers ◽  
Jean-Marie Lehn
Keyword(s):  
Metal Complexes ◽  
Driving Forces ◽  
Dynamic Networks ◽  
Dynamic Network ◽  
The Self ◽  
Self Assembling ◽  
Kinetic Trap ◽  
Sorting Process ◽  
Agonistic Relationships ◽  
The Stability

<div>Three imine-based metal complexes, having no overlap in terms of their compositions, have been simultaneously generated from the self-sorting of a constitutional dynamic library (CDL) containing three amines, three aldehydes and three metal salts. The hierarchical ordering of the stability of three metal complexes assembled and the leveraging of the antagonistic and agonistic relationships existing between the constituents within the constitutional dynamic network corresponding to the CDL were pivotal in achieving the desired sorting. The mechanism and the driving forces underlying the self-sorting process have been studied by NMR. The self-sorting of the Fe(II) and Zn(II) complexes was found to depend on an interplay between the thermodynamic driving forces and a kinetic trap involved in their assembling. These results also exemplify the concept of “simplexity” –the fact that the output of a self-assembling system may be simplified by increasing its initial compositional complexity—as the two complexes could self-sort only in the presence of the third pair of organic components, those of the Cu(I) complex.</div><br>

scholarly journals Self-Sorting of Two Imine-Based Metal Complexes: Balancing Kinetics and Thermodynamics in Constitutional Dynamic Networks

2019 ◽  
Author(s):  
Jean-François Ayme ◽  
Jean-Marie Lehn
Keyword(s):  
Metal Ions ◽  
Metal Complexes ◽  
Dynamic Networks ◽  
Tetrahedral Complex ◽  
Organic Components ◽  
Factors Influencing ◽  
Ligand Coordination ◽  
Sorting Process ◽  
Reversible Covalent ◽  
Metal Ligand

A major hurdle in the development of complex constitutional dynamic networks (CDNs) is the lack of strategies to simultaneously control the output of two (or more) interconnected dynamic processes over several species, namely reversible covalent imine bonds formation and dynamic metal-ligand coordination. We have studied in detail the factors influencing the fidelity of the self-sorting process (concentration, electronic and steric parameters of the organic components, nature of the metal cations) of 11 constitutional dynamic libraries containing two different amines, aldehydes and metals salts into two imine-based metal complexes, having no overlap in term of their compositions. In all the cases, the outcome of the process was primarily determined by the ability of the octahedral metal ions to select its pair of components from the initial pool of components, the composition of the weaker tetrahedral complex being imposed by the components rejected by the octahedral metal ions. Different octahedral metal ions required different level of precision in the “assembling instructions” provided by the organic components of the CDN to guide it towards a sorted output. The concentration of the reaction mixture, the electronic and steric properties of the initial components of the library were all found to influence the lifetime of unwanted metastable intermediates formed during the assembling of the two complexes.

scholarly journals Self-Sorting of Two Imine-Based Metal Complexes: Balancing Kinetics and Thermodynamics in Constitutional Dynamic Networks

2019 ◽  
Author(s):  
Jean-François Ayme ◽  
Jean-Marie Lehn
Keyword(s):  
Metal Ions ◽  
Metal Complexes ◽  
Dynamic Networks ◽  
Tetrahedral Complex ◽  
Organic Components ◽  
Factors Influencing ◽  
Ligand Coordination ◽  
Sorting Process ◽  
Reversible Covalent ◽  
Metal Ligand

A major hurdle in the development of complex constitutional dynamic networks (CDNs) is the lack of strategies to simultaneously control the output of two (or more) interconnected dynamic processes over several species, namely reversible covalent imine bonds formation and dynamic metal-ligand coordination. We have studied in detail the factors influencing the fidelity of the self-sorting process (concentration, electronic and steric parameters of the organic components, nature of the metal cations) of 11 constitutional dynamic libraries containing two different amines, aldehydes and metals salts into two imine-based metal complexes, having no overlap in term of their compositions. In all the cases, the outcome of the process was primarily determined by the ability of the octahedral metal ions to select its pair of components from the initial pool of components, the composition of the weaker tetrahedral complex being imposed by the components rejected by the octahedral metal ions. Different octahedral metal ions required different level of precision in the “assembling instructions” provided by the organic components of the CDN to guide it towards a sorted output. The concentration of the reaction mixture, the electronic and steric properties of the initial components of the library were all found to influence the lifetime of unwanted metastable intermediates formed during the assembling of the two complexes.

scholarly journals Chiral Self-Sorting in Truxene-Based Metallacages

Inorganics ◽  
2019 ◽  
Vol 8 (1) ◽  
pp. 1 ◽  
Author(s):  
Simon Séjourné ◽  
Antoine Labrunie ◽  
Clément Dalinot ◽  
Amina Benchohra ◽  
Vincent Carré ◽  
...  
Keyword(s):  
Solid State ◽  
The Self ◽  
X Ray ◽  
X Ray Crystallography ◽  
Self Assembling ◽  
Sorting Process ◽  
Non Covalent Interactions ◽  
Covalent Interactions

Two chiral face-rotating metalla-assembled polyhedra were constructed upon self-assembling achiral components, i.e., a tritopic ligand based on a truxene core (10,15-dihydro-5H-diindeno[1,2-a;1′,2′-c]fluorene) and two different hydroxyquinonato–bridged diruthenium complexes. Both polyhedra were characterized in solution as well as in the solid state by X-ray crystallography. In both cases, the self-sorting process leading to only two homo-chiral enantiomers was governed by non-covalent interactions between both truxene units that faced each other.

A Study on the Stability and Enzymatic Activity of Yeast Alcohol Dehydrogenase in Presence of the Self-Assembling Block Copolymer Poloxamer 407

2012 ◽  
Vol 167 (2) ◽  
pp. 298-313 ◽  
Author(s):  
Stefania Pucciarelli ◽  
Giulia Bonacucina ◽  
Franco Bernabucci ◽  
Marco Cespi ◽  
Giovanna Mencarelli ◽  
...  
Keyword(s):  
Block Copolymer ◽  
Alcohol Dehydrogenase ◽  
Enzymatic Activity ◽  
The Self ◽  
Poloxamer 407 ◽  
Yeast Alcohol Dehydrogenase ◽  
Self Assembling ◽  
The Stability

scholarly journals Cluster-based efficient information dissemination in dynamic networks

2018 ◽  
Vol 14 (3) ◽  
pp. 155014771876208
Author(s):  
Zhiwei Yang ◽  
Weigang Wu ◽  
Yong Li ◽  
Yishun Chen
Keyword(s):  
Information Dissemination ◽  
Dynamic Networks ◽  
Cluster Head ◽  
Dynamic Network ◽  
Network Models ◽  
Node Mobility ◽  
Dynamic Network Model ◽  
Dynamic Network Models ◽  
Efficient Information ◽  
The Stability

Dynamic network is an abstraction of networks with frequent topology changes arising from node mobility or other reasons. In this article, we first propose a dynamic network model, named ( T, L)-HiNet, to extend existing dynamic network models with clusters. ( T, L)-HiNet includes several properties defining the stability of cluster hierarchy in a dynamic network, including cluster head set, cluster member set and the connections among them. Based on ( T, L)-HiNet, we design several hierarchical information dissemination algorithms for different scenarios of dynamics. Furthermore, we extend the ( T, L)-HiNet model and corresponding algorithms in two directions, that is, stability of cluster head set and cluster size. The correctness of our algorithms is proved rigorously, and their performance is evaluated via both numerical analysis and simulations. The results show that compared with the algorithm recently proposed by Kuhn et al., our design can significantly reduce communication cost and also time cost.

The Role of Hydrophobicity in the Stability and pH-Switchability of (RXDX)4 and Coumarin-RXDX Conjugate β-Sheets

2020 ◽  
Author(s):  
Ryan Weber ◽  
Martin McCullagh
Keyword(s):  
Biological Imaging ◽  
Ph Sensing ◽  
Hydrophobic Residue ◽  
Ideal Candidate ◽  
Self Assembling ◽  
Sensing Applications ◽  
Β Sheets ◽  
The Stability ◽  
Dynamics Simulations

<p>pH-switchable, self-assembling materials are of interest in biological imaging and sensing applications. Here we propose that combining the pH-switchability of RXDX (X=Ala, Val, Leu, Ile, Phe) peptides and the optical properties of coumarin creates an ideal candidate for these materials. This suggestion is tested with a thorough set of all-atom molecular dynamics simulations. We first investigate the dependence of pH-switchabiliy on the identity of the hydrophobic residue, X, in the bare (RXDX)<sub>4</sub> systems. Increasing the hydrophobicity stabilizes the fiber which, in turn, reduces the pH-switchabilty of the system. This behavior is found to be somewhat transferable to systems in which a single hydrophobic residue is replaced with a coumarin containing amino acid. In this case, conjugates with X=Ala are found to be unstable and both pHs while conjugates with X=Val, Leu, Ile and Phe are found to form stable β-sheets at least at neutral pH. The (RFDF)<sub>4</sub>-coumarin conjugate is found to have the largest relative entropy value of 0.884 +/- 0.001 between neutral and acidic coumarin ordering distributions. Thus, we posit that coumarin-(RFDF)<sub>4</sub> containing peptide sequences are ideal candidates for pH-sensing bioelectronic materials.</p>

Simultaneous Generation of a [2×2] Grid-like Complex and a Linear Double Helicate: A Three-Level Self-Sorting Process

2019 ◽  
Author(s):  
Jean-François Ayme ◽  
Jean-Marie Lehn ◽  
Corinne Bailly ◽  
Lydia Karmazin
Keyword(s):  
Metal Complexes ◽  
Mass Spectroscopy ◽  
Metal Salts ◽  
Simultaneous Generation ◽  
X Ray ◽  
X Ray Crystallography ◽  
Sorting Process

<div>Two constitutional dynamic libraries (CDLs)—each containing two amines, two dialdehydes and two metal salts—have been found to self-sort, generating two pairs of imine-based metallosupramolecular architectures sharing no component, a [2×2] grid-like complex and a linear double helicate. These CDLs provided unique examples of a three-level self-sorting process, as only two imine-based ligand constituents, two metal complexes and two architectures were selected during their assembling out of all the possible combinations of their initial components. The metallosupramolecular architectures assembled were characterized by NMR, mass spectroscopy, and X-ray crystallography.</div>

Directive Effect of Chain Length in Modulating Peptide Nano-assemblies

2020 ◽  
Vol 27 (9) ◽  
pp. 923-929
Author(s):  
Gaurav Pandey ◽  
Prem Prakash Das ◽  
Vibin Ramakrishnan
Keyword(s):  
Electron Microscopy ◽  
Amino Acids ◽  
Light Scattering ◽  
Chain Length ◽  
Self Assembly ◽  
The Self ◽  
Ionic Charge ◽  
Self Assembling ◽  
Biophysical Techniques

Background: RADA-4 (Ac-RADARADARADARADA-NH2) is the most extensively studied and marketed self-assembling peptide, forming hydrogel, used to create defined threedimensional microenvironments for cell culture applications. Objectives: In this work, we use various biophysical techniques to investigate the length dependency of RADA aggregation and assembly. Methods: We synthesized a series of RADA-N peptides, N ranging from 1 to 4, resulting in four peptides having 4, 8, 12, and 16 amino acids in their sequence. Through a combination of various biophysical methods including thioflavin T fluorescence assay, static right angle light scattering assay, Dynamic Light Scattering (DLS), electron microscopy, CD, and IR spectroscopy, we have examined the role of chain-length on the self-assembly of RADA peptide. Results: Our observations show that the aggregation of ionic, charge-complementary RADA motifcontaining peptides is length-dependent, with N less than 3 are not forming spontaneous selfassemblies. Conclusion: The six biophysical experiments discussed in this paper validate the significance of chain-length on the epitaxial growth of RADA peptide self-assembly.

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