Self-Assembly of Silver Metal Clusters of Small Atomicity on Cyclic Peptide Nanotubes

Cuerva, Miguel; García‐Fandiño, Rebeca; Vázquez–Vázquez, C.; López‐Quintela, M. Arturo; Montenegro, Javier; Granja, Juan R.

doi:10.1021/acsnano.5b03445

Cited by 50 publications

(41 citation statements)

References 45 publications

(232 reference statements)

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“…However, owing to the distance mismatch between β‐sheets and π–π stacks, the intercalation of pyrene moieties allows the one‐dimensional hierarchical arrangement of the corresponding micrometer‐sized tubular bundles (Figure A, bottom) . As previously reported, the pH control of solutions of CP1 allowed peptide self‐assembly assisted by pyrene stacking as shown by the quenching and the bathochromic shift of the fluorescence emission due to excimer formation …”

Section: Resultssupporting

confidence: 58%

Spatially Controlled Supramolecular Polymerization of Peptide Nanotubes by Microfluidics

Méndez‐Ardoy

Bayón‐Fernández

et al. 2020

Angewandte Chemie

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Despite the importance of spatially resolved selfassembly for molecular machines,t he spatial control of supramolecular polymerization with synthetic monomers had not been experimentally established. Now,amicrofluidicregulated tandem process of supramolecular polymerization and droplet encapsulation is used to control the position of selfassembled microfibrillar bundles of cyclic peptide nanotubes in water droplets.T his method allows the precise preferential localization of fibers either at the interface or into the core of the droplets.U Vabsorbance,c ircular dichroism and fluorescence microscopyindicated that the microfluidic control of the stimuli (changes in pH or ionic strength) can be employed to adjust the packingd egree and the spatial position of microfibrillar bundles of cyclic peptide nanotubes.Additionally,this spatially organized supramolecular polymerization of peptide nanotubes was applied in the assembly of highly ordered twodimensional droplet networks.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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Section: Resultssupporting

confidence: 58%

Spatially Controlled Supramolecular Polymerization of Peptide Nanotubes by Microfluidics

Méndez‐Ardoy

Bayón‐Fernández

et al. 2020

Angewandte Chemie

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“…9,10 In addition, Ag clusters exhibit a high affinity to undergo covalent binding to biomolecules, which makes them ideal candidates for the preparation of cluster-organic aggregates. [11][12][13] As an example, DNA origami scaffolds have been used in order to assemble metal nanoclusters in a precisely defined threedimensional architecture. 14,15 Various organic ligands can help to stabilize clusters as it has been shown in several recent studies.…”

Section: Introductionmentioning

confidence: 99%

Excitonic Properties of Ordered Metal Nanocluster Arrays: 2D Silver Clusters at Multiporphyrin Templates

2016

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The design of ordered arrays of metal nanoclusters such as for example 2D cluster organic frameworks might open a new route towards the development of materials with tailored optical properties. Such systems could serve as plasmonically enhanced light-harvesting materials, sensors or catalysts. We present here a theoretical approach for the simulation of the optical properties of ordered arrays of metal clusters that is based on the ab initio parametrized Frenkel exciton model. We demonstrate that small atomically precise silver clusters can be assembled in one-and two-dimensional arrays on suitably designed porphyrin templates exhibiting remarkable optical properties. By employing explicit TDDFT calculations on smaller homologs, we show that the intrinsic optical properties of metal clusters are largely preserved but undergo J-and H-type excitonic coupling that results in controllable splitting of their excited states.Furthermore, ab initio parameterized Frenkel exciton model calculations allow us to predict an energetic splitting of up to 0.77 eV in extended two-dimensional square arrays and 0.79 eV in tilted square aggregates containing up to 25 cluster-porphyrin subunits.

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“…Computational techniques afford a level of atomistic resolution that cannot be easily accessed by other experimental techniques, providing information that can help to understand and describe the interactions that are occurring in supramolecular systems. In particular, computational simulations of CPs and SCPNs constitute a valuable complement to the experimental investigations and provide further insights into the structural properties of these compounds, as has been demonstrated in our group during the last years . Thus, using a combined experimental/computational (in vitro/in silico) approach, we describe, for the first time, the stability and structure of d,l ‐α,δ‐CPs, paying special attention to the parallel or the antiparallel interaction that can be adopted in polymeric systems.…”

Section: Introductionmentioning

confidence: 93%

Parallel Versus Antiparallel β‐Sheet Structure in Cyclic Peptide Hybrids Containing γ‐ or δ‐Cyclic Amino Acids

Calvelo

Lamas

Guerra

et al. 2020

Chemistry A European J

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Cyclic peptides with disc-shaped structures have emerged as potent building blocks for the preparation of new biomaterialsi nf ields ranging from biological to material science. In this work, we analyze in depth the self-assembling properties of an ew type of cyclic peptidesb ased on the alternation of a-residues and cyclic d-amino acids (a,d-CPs). To examine the preferred stacking properties adopted by cyclic peptides bearing this type of amino acids, we carried out as ynergistic in vitro/in silico approximation by using simple dimeric models and then extended to nanotubes. Althought hesen ew cyclic peptides( a,d-CPs) can interact either in ap arallelo ra ntiparallel fashion, our results confirm that although the parallel b-sheet is more stable, it can be switched to the antiparallel stacking by choosing residues that can establish favorable cross-strand interactions. Moreover, the subsequent comparison by using the same methodology but applied to a,g-CPs models, up to the moment assumeda sa ntiparallel-like d,l-a-CPs, led to unforeseen conclusions that put into question preliminaryc onjecturesa bout these systems. Surprisingly,t hey tend to adopt ap arallel b-sheet directed by the skeleton interactions. These results imply ac hange of paradigm with respect to cyclic peptided esigns that shouldb ec onsidered for dimers and nanotubes.Scheme1.Peptide nanotube models formed by stacking of cyclicpeptides: a) d,l-a-CP andc )b-CP (bottom) in af lat conformation and b) structure of someC Ps containing g-Acas (a,g-CP,3a,g-CP,and g-CP,f rom left to right) that canalso form nanotubes. Models of antiparallel, for d,l-a-CPs, or parallel, for d,l-a-CPs and for b-CPs, type b-sheet structures are also illustrated.Scheme2.Structure of the d-Ach and model of b-sheeti nteractions (parallel at the top or antiparallel at the bottom) of d,l-peptide strands upon intercalation of a d-Ach after each amino acid of identical chirality ( d,left) or after each residue (d,l-a,d-CP,right). Carbonyland NH groups are denotedin blue and red, respectively, depending on their relative orientation in the disc-shaped conformation;for a-residuesred color was assigned to d-residues whereas blue color was attributed to l-residues, respectively.Alternatively, d-Achs have the carbonyl and NH groups always with different colors, one in red pointing in the same direction as the d-residuesa nd the othero ne in blue as the l-amino acids.Scheme6.Model of nanotube SCPN9 obtained by the assembling CP9 and,o nt he right, the computer-generated model in whicha ll the amino acidss ide chains were changed to methyl groups. At the bottom,t op-view model of the threedifferent dimeric forms for each type of interactions (parallela nd antiparallel) to evaluate the side chaincross-strand interactions between two consecutive cyclic peptides. Only in the antiparallel form Ccan two salt-bridged interactionsb ee stablished betweenG lu and Lysside chains.His-Argpairs are also observed in other stacking models (E, A, or F) but in these cases, the alignment of Arg residues t...

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Self-Assembly of Silver Metal Clusters of Small Atomicity on Cyclic Peptide Nanotubes

Cited by 50 publications

References 45 publications

Spatially Controlled Supramolecular Polymerization of Peptide Nanotubes by Microfluidics

Spatially Controlled Supramolecular Polymerization of Peptide Nanotubes by Microfluidics

Excitonic Properties of Ordered Metal Nanocluster Arrays: 2D Silver Clusters at Multiporphyrin Templates

Parallel Versus Antiparallel β‐Sheet Structure in Cyclic Peptide Hybrids Containing γ‐ or δ‐Cyclic Amino Acids

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