Superchiral Pd3L6 Coordination Complex and Its Reversible Structural Conversion into Pd3L3Cl6 Metallocycles

Jurček, Ondřej; Bonakdarzadeh, Pia; Kalenius, Elina; Linnanto, Juha; Groessl, Michael; Knochenmuss, Richard; Ihalainen, Janne A.; Rissanen, Kari

doi:10.1002/anie.201506539

Cited by 57 publications

(14 citation statements)

References 48 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…2+ formed after addition of n Bu4NCl. 64 Figure reproduced with We must keep in mind that supramolecular systems can be dynamic in solution and often have components with only modest association constants. Thus, if the initial system concentration is low, it can dissociate (to some extent) into free individual components or lower nuclearity species.…”

Section: ]mentioning

confidence: 99%

Ion mobility–mass spectrometry of supramolecular complexes and assemblies

2018

Self Cite

View full text Add to dashboard Cite

Despite their structural and functional differences, synthetic supramolecular assemblies share many similarities with biological ones, especially enzymes. The assemblies can be on the same length scales, and their structures and guest binding are typically governed by non-covalent interactions. Thus, only relatively weak interactions define the shape of a synthetic supramolecule or a protein's secondary and tertiary structure, such that the resulting dynamism makes structure elucidation challenging. In the case of biomolecules such as peptides, proteins, glycans and lipids, this has often been tackled using ion mobility-mass spectrometry (IM-MS), whereby analyte ions are separated according to their gasphase mobility as well as their mass-to-charge ratio. IM-MS is an established method in 'omics', separation sciences, and small molecule structural chemistry but has only recently grown in popularity for the study of synthetic supramolecular assemblies in the gas phase. This Perspective describes IM-MS techniques and how they help us understand the structures of molecular self-assemblies, host-guest complexes and metallosupramolecular complexes.

show abstract

Section: ]mentioning

confidence: 99%

Ion mobility–mass spectrometry of supramolecular complexes and assemblies

2018

Self Cite

View full text Add to dashboard Cite

show abstract

“…Furthermore, direct evidence for a shrinking and expansion of the cages upon addition of the short and long guests, respectively, came from trapped ion mobility ESI-TOF mass spectrometry (timsTOF), which indicated a smaller gas phase collisional cross-section for G2@C2 P (701 2 ) than for G3@C2 P (705 2 ), even in a mixture of both host-guest complexes ( Figure 5 d and Figure S27). [26] We repeated the CD experiment with azobenzene-based guest G4, [27] either in its cis or trans photoisomeric form ( Figure 5 b). Remarkably, the effect of the band intensity decrease/increase could be reproduced and allows differentiation between the cis and the trans form of achiral azobenzene by CD spectroscopy, keeping in mind that the free guest itself shows no CD effect.…”

Section: Angewandte Chemiementioning

confidence: 99%

Chiral Self‐Discrimination and Guest Recognition in Helicene‐Based Coordination Cages

2019

View full text Add to dashboard Cite

Chiral nanosized confinements play a major role for enantioselective recognition and reaction control in biological systems. Supramolecular self‐assembly gives access to artificial mimics with tunable sizes and properties. Herein, a new family of [Pd2L4] coordination cages based on a chiral [6]helicene backbone is introduced. A racemic mixture of the bis‐monodentate pyridyl ligand L1 selectively assembles with PdII cations under chiral self‐discrimination to an achiral meso cage, cis‐[Pd2L1P2L1M2]. Enantiopure L1 forms homochiral cages [Pd2L1P/M4]. A longer derivative L2 forms chiral cages [Pd2L2P/M4] with larger cavities, which bind optical isomers of chiral guests with different affinities. Owing to its distinct chiroptical properties, this cage can distinguish non‐chiral guests of different lengths, as they were found to squeeze or elongate the cavity under modulation of the helical pitch of the helicenes. The CD spectroscopic results were supported by ion mobility mass spectrometry.

show abstract

“…According to a modified literature procedure, the carboxylic acid of LCA was selectively protected [ 26 ]. LCA ( 1 , 1.0 equivalents (eq.))…”

Section: Methodsmentioning

confidence: 99%

Nanotherapeutics Containing Lithocholic Acid-Based Amphiphilic Scorpion-Like Macromolecules Reduce In Vitro Inflammation in Macrophages: Implications for Atherosclerosis

Moretti

Chmielowski

et al. 2018

Nanomaterials

View full text Add to dashboard Cite

Previously-designed amphiphilic scorpion-like macromolecule (AScM) nanoparticles (NPs) showed elevated potency to counteract oxidized low-density lipoprotein (oxLDL) uptake in atherosclerotic macrophages, but failed to ameliorate oxLDL-induced inflammation. We designed a new class of composite AScMs incorporating lithocholic acid (LCA), a natural agonist for the TGR5 receptor that is known to counteract atherosclerotic inflammation, with two complementary goals: to simultaneously decrease lipid uptake and inhibit pro-inflammatory cytokine secretion by macrophages. LCA was conjugated to AScMs for favorable interaction with TGR5 and was also hydrophobically modified to enable encapsulation in the core of AScM-based NPs. Conjugates were formulated into negatively charged NPs with different core/shell combinations, inspired by the negative charge on oxLDL to enable competitive interaction with scavenger receptors (SRs). NPs with LCA-containing shells exhibited reduced sizes, and all NPs lowered oxLDL uptake to <30% of untreated, human derived macrophages in vitro, while slightly downregulating SR expression. Pro-inflammatory cytokine expression, including IL-1β, IL-8, and IL-10, is known to be modulated by TGR5, and was dependent on NP composition, with LCA-modified cores downregulating inflammation. Our studies indicate that LCA-conjugated AScM NPs offer a unique approach to minimize atherogenesis and counteract inflammation.

show abstract

Superchiral Pd₃L₆ Coordination Complex and Its Reversible Structural Conversion into Pd₃L₃Cl₆ Metallocycles

Cited by 57 publications

References 48 publications

Ion mobility–mass spectrometry of supramolecular complexes and assemblies

Ion mobility–mass spectrometry of supramolecular complexes and assemblies

Chiral Self‐Discrimination and Guest Recognition in Helicene‐Based Coordination Cages

Nanotherapeutics Containing Lithocholic Acid-Based Amphiphilic Scorpion-Like Macromolecules Reduce In Vitro Inflammation in Macrophages: Implications for Atherosclerosis

Contact Info

Product

Resources

About