Solid state conformational behavior and interactions of a series of aromatic oligoamide foldamers

The topic of this thesis is aromatic oligoamide foldamers. The literary review of the thesis discusses the general features of foldamers and their design and then focuses on the specific examples of aromatic oligoamide foldamers. The experimental part of the thesis discusses the design and preparation of a family of aromatic oligoamide foldamers that can adopt a helical conformation. The folding is directed by intramolecular hydrogen bonding and stabilized by intramolecular aromatic interactions. The focus of the thesis is the analysis of the solid state conformations of ten foldamer analogues. The analysis is based on forty different crystal structures which are determined using single crystal X-ray diffraction. In selected cases the solution behavior of the compounds is analyzed using NMR spectroscopy, and the conformations are compared to DFT calculations. Three types of aromatic oligoamide foldamers were synthesized: a benzene foldamer and its sulfonamide analogue, where two of the amide bonds were replaced by a sulfonamide bond, and a series of pyridine foldamers. The benzene foldamer, while able to fold in a fairly open helical conformation, was found to have high flexibility that hinders the design of consistently folding molecules. DFT calculations showed that the sulfonamide foldamer could fold in a highly folded helical conformation, but the folding was not observed experimentally. Pyridine foldamers have a central 2,6-pyridine core unit that is planar and directs the adjacent amide N-H groups towards the inner face of the folded conformation. The first pyridine foldamer, the analogue of the benzene foldamer, showed improved folding predictability and solubility. The other pyridine foldamers are asymmetric analogues designed to study the effect of the different electron density donating properties, as well as, the presence, size and bulkiness of the substituent to the folding properties of the compounds

Orgaanisten yhdisteiden kiinteän tilan rakennemääritysmenetelmät

Pro gradu -tutkielmassa käydään läpi 16 yleistä orgaanisten yhdisteiden kiinteän tilan rakennemääritysmenetelmää. Erityistä huomiota on tutkielmassa osoitettu röntgendiffraktiolle, kiinteän tilan NMR-spektroskopialle ja infrapunaspektroskopialle. Erikoistyössä valmistettiin kaksi uutta amidofoldameeriä ja yksi uusi sulfonyylifoldameeri. Valmistettujen yhdisteiden ominaisuuksia tutkittiin ja niitten rakenteet määritettiin. Lisäksi määritettiin yhden muodostetun fluorikompleksin rakenne

CCDC 1455102: Experimental Crystal Structure Determination

WAFYAG : N,N'-(((1,3-phenylenedisulfonyl)bis(azanediyl))bis(2,1-phenylene))dibenzamide perdeuteroacetone solvate Space Group: C2/c, Cell: a 24.9217(15)Å b 6.9550(5)Å c 20.6193(15)Å, α 90° β 105.782(7)° γ 90°. Work published 2016 via Cambridge Crystallographic Data Centre

The Missing Member of the Partially O-Alkylated Resorcinarene Family: Synthesis and Conformation of Methyl Tetramethoxy Resorcinarene

An improved Lewis acid catalyzed synthesis method for methyl tetramethoxy resorcinarene is described, which produced the missing lower rim methyl derivative of this partially O-alkylated resorcinarene family. Structural characterization by means of variable temperature NMR experiments and single crystal X-ray diffraction studies furthermore revealed that the resorcinarene core adopts different conformations in the solid state and in solution.peerReviewe

Cation binding resorcinarene bis-crowns: the effect of lower rim alkyl chain length on crystal packing and solid lipid nanoparticles

A group of seven resorcinarene bis-crown ethers (CNBC5) with two polyether bridges at the upper rim and either propyl, butyl, pentyl, heptyl, nonyl, decyl or undecyl groups at the lower rim were synthesized and their binding properties with Cs+ were investigated by NMR titration. The bis-crowns form 1:2 complexes with Cs+ with binding constants of logK 4–5. Crystal structures of bis-crowns and their Cs+ and K+ complexes were studied and different packing motifs were found depending on the alkyl chain length. Short ethyl, propyl and butyl alkyl chains gave a layer or pillar packing where the polar and non-polar regions cannot be distinguished, whereas longer pentyl and decyl chains formed bilayers. Amphiphilic properties and self-assembly in water were studied by preparing solid lipid nanoparticles (SLNs) from the bis-crowns. All investigated compounds formed stable SLNs showing amphiphilic character, which in the case of the short chain bis-crowns probably arises from their locked boat conformation separating the polar face of the molecule from the non-polar face.peerReviewe

Conformational properties and folding analysis of a series of seven oligoamide foldamers

33 crystal structures (11 unsolvated and 22 solvates) of a series of seven oligoamide foldamers were analysed. The crystal structures revealed that despite the structural and environmental differences the series of foldamers prefer only two general conformations, a protohelical @-conformation and a sigmoidal S-conformation. Both conformations also have preferred crystal packing motifs and solvate forming tendencies. Hydrogen bonding was found to be the most decisive factor in conformational preference, but steric properties, the type of the peripheral substituents, as well as solvent and aromatic interactions were also found to have an effect on the conformational details and crystal form.peerReviewe

Oligoamide Foldamers as Helical Chloride Receptors : the Influence of Electron-Withdrawing Substituents on Anion-Binding Interactions

The anion‐binding properties of three closely related oligoamide foldamers were studied using NMR spectroscopy, isothermal titration calorimetry and mass spectrometry, as well as DFT calculations. The 1H NMR spectra of the foldamers in [D6]acetone solution revealed partial preorganization by intramolecular hydrogen bonding, which creates a suitable cavity for anion binding. The limited size of the cavity, however, enabled efficient binding by the inner amide protons only for the chloride anion resulting in the formation of a thermodynamically stable 1:1 complex. All 1:1 chloride complexes displayed a significant favourable contribution of the entropy term. Most likely, this is due to the release of ordered solvent molecules solvating the free foldamer and the anion to the bulk solution upon complex formation. The introduction of electron‐withdrawing substituents in foldamers 2 and 3 had only a slight effect on the thermodynamic constants for chloride binding compared to the parent receptor. Remarkably, the binding of chloride to foldamer 3 not only produced the expected 1:1 complex but also open aggregates with 1:2 (host:anion) stoichiometry.peerReviewe

The Missing Member of the Partially <i>O</i>‑Alkylated Resorcinarene Family: Synthesis and Conformation of Methyl Tetramethoxy Resorcinarene

An improved Lewis acid catalyzed synthesis method for methyl tetramethoxy resorcinarene is described, which produced the missing lower rim methyl derivative of this partially <i>O</i>-alkylated resorcinarene family. Structural characterization by means of variable temperature NMR experiments and single crystal X-ray diffraction studies furthermore revealed that the resorcinarene core adopts different conformations in the solid state and in solution

The Missing Member of the Partially <i>O</i>‑Alkylated Resorcinarene Family: Synthesis and Conformation of Methyl Tetramethoxy Resorcinarene

An improved Lewis acid catalyzed synthesis method for methyl tetramethoxy resorcinarene is described, which produced the missing lower rim methyl derivative of this partially <i>O</i>-alkylated resorcinarene family. Structural characterization by means of variable temperature NMR experiments and single crystal X-ray diffraction studies furthermore revealed that the resorcinarene core adopts different conformations in the solid state and in solution

'I'll get by with a little help from my friends' Information for friends of people with dementia

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