Halogen bonding modulates hydrogel formation from Fmoc amino acids

Pizzi, Andrea; Lascialfari, Luisa; Demitri, Nicola; Bertolani, Arianna; Maiolo, Daniele; Carretti, Emiliano; Metrangolo, Pierangelo

doi:10.1039/c7ce00031f

Cited by 38 publications

(39 citation statements)

References 34 publications

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“…As a result, the directed assembly of compositionally and structurally complex architectures requires a thorough understanding of the way in which complementary and competing forces eventually lead to a stable solid-state architecture [6,7]. Against this background, our goal was to establish reliable and robust avenues for the design and synthesis of crystalline metal-containing materials by encoding each building-block with structural-preferences that lead to "programmable" and predictable assembly [8][9][10].…”

Section: Introductionmentioning

confidence: 99%

The Role of Halogen Bonding in Controlling Assembly and Organization of Cu(II)-Acac Based Coordination Complexes

et al. 2017

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Abstract:In order to explore the use of non-covalent interactions in the deliberate assembly of metal-supramolecular architectures, a series of β-diketone based ligands capable of simultaneously acting as halogen-bond donors and chelating ligands were synthesized. The three ligands, L1, L2, and L3, carry ethynyl-activated chlorine, bromine, and iodine atoms, respectively and copper(II) complexes of all three ligands were crystallized from different solvents, acetonitrile, ethyl acetate, and nitromethane in order to study specific ligand-solvent interaction. The free ligands L2 and L3, with more polarizable halogen atoms, display C-X· · · O halogen bonds in the solid state, whereas the chloro-analogue (L1) does not engage in halogen bonding. Both acetonitrile and ethyl acetate act as halogen-bond acceptors in Cu(II)-complexes of L2 and L3 whereas nitromethane is present as a 'space-filling' guest without participating in any significant intermolecular interactions in Cu(II)-complexes of L2. L3, which is decorated with an iodoethynyl moiety and consistently engages in halogen-bonds with suitable acceptors. This systematic structural analysis allows us to rank the relative importance of a variety of electron-pair donors in these metal complexes.

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Section: Introductionmentioning

confidence: 99%

The Role of Halogen Bonding in Controlling Assembly and Organization of Cu(II)-Acac Based Coordination Complexes

et al. 2017

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“…In the field of crystal engineering driven by halogen bond, it has been observed that the replacement of an iodine atom with a bromine atom in a molecule weakly affects its overall crystal packing leading, in most of the cases, to isostructural systems . Based on this consideration, we did not expect remarkable differences in the overall crystal packing between KLVFF(Br) and its iodinated derivative.…”

Section: Resultsmentioning

confidence: 69%

Crystallographic insights into the self‐assembly of KLVFF amyloid‐beta peptides

et al. 2018

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Amyloidogenic peptide fragment KLVFF (H N-Lys-Leu-Val-Phe-Phe-COOH, Aβ ), the core-sequence of the polypeptide Aβ40, is a well-studied model for amyloid formation. However, due to its low crystallinity, detailed atomic information of KLVFF structure is lacking. Here we report the high-resolution single-crystal X-ray structure of two monohalogenated KLVFF derivatives, KLVFF(I) and KLVFF(Br). The obtained results highlight how halogenation is a good strategy to promote crystallization and facilitate the phase determination of KLVFF(I) and KLVFF(Br) fragments. Detailed structural studies on the packing features of both monohalogenated derivatives reveal the role of the halogen atoms showing that when they are positioned on the Phe aromatic moiety at the C-terminus they do not form halogen bonds and thus do not produce any extra stabilization of the β-sheet in the self-assembly process. The structural evidences gained from these studies corroborate the various polymorphic nanostructures of the halogenated variants of KLVFF and confirm the possibility to use halogenation as innovative strategy to tune the morphology of this pentapeptide.

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“…Additionally, it is worthy of mention that the presence of halogens affects the supramolecular patterns in the Fmoc-AA family. In particular, in XATKEL (Pizzi et al, 2017), C-IÁ Á Á interactions between an I atom and fluorenyl [IÁ Á Á(centroid of phenyl ring) distance is 3.829 Å and C-IÁ Á Á(centroid of phenyl ring) angle is 165.27 ] give rise to the formation of supramolecular rings. In XATJAG (Pizzi et al, 2017), those rings are created by C-BrÁ Á Á interactions.…”

Section: Interaction Typementioning

confidence: 99%

“…In particular, in XATKEL (Pizzi et al, 2017), C-IÁ Á Á interactions between an I atom and fluorenyl [IÁ Á Á(centroid of phenyl ring) distance is 3.829 Å and C-IÁ Á Á(centroid of phenyl ring) angle is 165.27 ] give rise to the formation of supramolecular rings. In XATJAG (Pizzi et al, 2017), those rings are created by C-BrÁ Á Á interactions. Thus, supramolecular halogenated motifs are interchangeable with molecular halogenated synthons.…”

Section: Interaction Typementioning

confidence: 99%

“…In the second section, a comprehensive comparative analysis and a hierarchy of the intermolecular interactions in all known relevant Fmoc-AA structures, as retrieved from the Cambridge Structural Database (CSD; Version 5.40, update February 2019; Groom et al, 2016) (see Schemes S1 and S2 in the supporting information), are considered. Generally, we divided privileged Fmoc-Tyr/ Phe derivatives into the following groups: A -containing a substituent O atom in the phenyl ring [(1), CAMLEK (Fichman et al, 2016), INEJEQ (Clegg & Elsegood, 2003), OGIYAG (Draper et al, 2015) and OGOGIA (Young & Kiessling, 2002)]; B -without substituents in the phenyl ring [OGIXOT, EKEWUM (Clegg & Elsegood, 2003), NUBPEH , OGIXUZ (Draper et al, 2015) and VERXUO (Rajbhandary et al, 2018)]; C -with an additional chain as substituent in the molecular backbone [MOXSUP (Scroggs et al, 2015) and DULLAZ (Wang et al, 2015)]; Dcontaining other substituents in the phenyl ring [UQIYUQ, UQOGUE (Liyanage & Nilsson, 2016) and WATSIU01 (Stefanowicz et al, 2006)]; E -including halogen atoms (XATJAG, XATJEK, XATKEL and XATKIP;Pizzi et al, 2017). Notably, OGOGIA, INEJEQ and EKEWUM possess a modified -COOH group.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis, experimental andin silicostudies ofN-fluorenylmethoxycarbonyl-O-tert-butyl-N-methyltyrosine, coupled with CSD data: a survey of interactions in the crystal structures of Fmoc–amino acids

Bojarska

Remko²,

Madura

et al. 2020

Acta Crystallogr C

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Recently, fluorenylmethoxycarbonyl (Fmoc) amino acids (e.g. Fmoc–tyrosine or Fmoc–phenylalanine) have attracted growing interest in biomedical research and industry, with special emphasis directed towards the design and development of novel effective hydrogelators, biomaterials or therapeutics. With this in mind, a systematic knowledge of the structural and supramolecular features in recognition of those properties is essential. This work is the first comprehensive summary of noncovalent interactions combined with a library of supramolecular synthon patterns in all crystal structures of amino acids with the Fmoc moiety reported so far. Moreover, a new Fmoc‐protected amino acid, namely, 2‐{[(9H‐fluoren‐9‐ylmethoxy)carbonyl](methyl)amino}‐3‐{4‐[(2‐hydroxypropan‐2‐yl)oxy]phenyl}propanoic acid or N‐fluorenylmethoxycarbonyl‐O‐tert‐butyl‐N‐methyltyrosine, Fmoc‐N‐Me‐Tyr(t‐Bu)‐OH, C29H31NO5, was successfully synthesized and the structure of its unsolvated form was determined by single‐crystal X‐ray diffraction. The structural, conformational and energy landscape was investigated in detail by combined experimental and in silico approaches, and further compared to N‐Fmoc‐phenylalanine [Draper et al. (2015). CrystEngComm, 42, 8047–8057]. Geometries were optimized by the density functional theory (DFT) method either in vacuo or in solutio. The polarizable conductor calculation model was exploited for the evaluation of the hydration effect. Hirshfeld surface analysis revealed that H…H, C…H/H…C and O…H/H…O interactions constitute the major contributions to the total Hirshfeld surface area in all the investigated systems. The molecular electrostatic potentials mapped over the surfaces identified the electrostatic complementarities in the crystal packing. The prediction of weak hydrogen‐bonded patterns via Full Interaction Maps was computed. Supramolecular motifs formed via C—H…O, C—H…π, (fluorenyl)C—H…Cl(I), C—Br…π(fluorenyl) and C—I…π(fluorenyl) interactions are observed. Basic synthons, in combination with the Long‐Range Synthon Aufbau Modules, further supported by energy‐framework calculations, are discussed. Furthermore, the relevance of Fmoc‐based supramolecular hydrogen‐bonding patterns in biocomplexes are emphasized, for the first time.

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Halogen bonding modulates hydrogel formation from Fmoc amino acids

Cited by 38 publications

References 34 publications

The Role of Halogen Bonding in Controlling Assembly and Organization of Cu(II)-Acac Based Coordination Complexes

The Role of Halogen Bonding in Controlling Assembly and Organization of Cu(II)-Acac Based Coordination Complexes

Crystallographic insights into the self‐assembly of KLVFF amyloid‐beta peptides

Synthesis, experimental andin silicostudies ofN-fluorenylmethoxycarbonyl-O-tert-butyl-N-methyltyrosine, coupled with CSD data: a survey of interactions in the crystal structures of Fmoc–amino acids

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