Search results for "Pram"
showing 10 items of 1064 documents
Metal ions modulate thermal aggregation of betalactoglobulin: a join chemical and physical characterization
2014
Abstract Molecular basis of the role played by Cu 2 + and Zn 2 + ions during the thermal aggregation processes of beta-lactoglobulin (BLG) was studied by using a joint application of different techniques. In particular, Raman spectroscopy was very useful in identifying the different effects caused by the two metals at molecular level (i.e. changes in His protonation state, disulfides bridge conformation, and micro-environment of aromatic residues), evidencing the primary importance of the protein charge distribution during the aggregation process. Both metal ions are able to act on this factor and favor the protein aggregation, but Zn 2 + is able to alter the natural conformational state of…
Recent Advances in Halogen Bonded Assemblies with Resorcin[4]arenes
2020
Resorcinarenes are cavity-containing compounds when in the crown conformation, from the calixarene family of concave compounds. These easy to synthesize macrocycles can be decorated at the upper rim through the eight hydroxyl groups and/or the 2-position of the aromatic ring. They are good synthons in supramolecular chemistry leading to appealing assemblies such as open-inclusion complexes, capsules and tubes through multiple weak interactions with various guests. Halogen bonding (XB) is a highly directional non-covalent interaction by an electron-deficient halogen atom as a donor that interacts with a Lewis base, the XB acceptor. This tutorial review provides an overview of recent advances…
Cocrystal trimorphism as a consequence of the orthogonality of halogen- and hydrogen-bonds synthons.
2019
True trimorphic cocrystals, i.e. multi-component molecular crystals of identical composition that exhibit three polymorphic structures, are exceedingly rare and so far no halogen-bonded cocrystal system has been reported to exhibit trimorphism. Here we describe a unique example of a trimorphic cocrystal exhibiting both hydrogen and halogen bonds in which the differences between polymorphs reveal their orthogonality, evident by the apparently independent variation of well-defined hydrogen- and halogen-bonded motifs. peerReviewed
Nano-sized I12L6 Molecular Capsules Based on the [N⋅⋅⋅I+⋅⋅⋅N] Halogen Bond
2017
Summary Self-assembly of pre-organized subunits with a concave overall shape is an effective strategy for the synthesis of supramolecular capsules. We report the synthesis of a cavitand-based hexameric capsule held together solely by 12 robust [N⋅⋅⋅I + ⋅⋅⋅N] halogen bonds and its characterization in solution and in the gas phase via 1 H NMR spectroscopy, diffusion-ordered nuclear magnetic resonance spectroscopy (DOSY), and electrospray ionization mass spectrometry. The [N⋅⋅⋅I + ⋅⋅⋅N] halogen-bonded hexameric capsule was efficiently synthesized from the isolobal metallosupramolecular Ag + capsule by application of the [N⋅⋅⋅Ag + ⋅⋅⋅N] → [N⋅⋅⋅I + ⋅⋅⋅N] cation-exchange reaction.
Surprising solvent-induced structural rearrangements in large [N⋯I+⋯N] halogen-bonded supramolecular capsules
2018
Coordinative halogen bonds have recently gained interest for the assembly of supramolecular capsules. Ion mobility-mass spectrometry and theoretical calculations now reveal the well-defined gas-phase structures of dimeric and hexameric [N...I+...N] halogen-bonded capsules with counterions located inside their cavities as guests. The solution reactivity of the large hexameric capsule shows the intriguing solvent-dependent equilibrium between the hexamer and an unprecedented pentameric [N...I+...N] halogen-bonded capsule, when the solvent is changed from chloroform to dichloromethane. The intrinsic flexibility of the cavitands enables this novel structure to adopt a pseudo-trigonal bipyramida…
Halogen bonding and host–guest chemistry between N-alkylammonium resorcinarene halides, diiodoperfluorobutane and neutral guests
2019
Single crystal X-ray structures of halogen-bonded assemblies formed between host N-hexylammonium resorcinarene bromide (1) or N-cyclohexylammonium resorcinarene chloride (2), and 1,4-diiodooctafluorobutane and accompanying small solvent guests (methanol, acetonitrile and water) are presented. The guests’ inclusion affects the geometry of the cavity of the receptors 1 and 2, while the divalent halogen bond donor 1,4-diiodooctafluorobutane determines the overall nature of the halogen bond assembly. The crystal lattice of 1 contains two structurally different dimeric assemblies A and B, formally resulting in the mixture of a capsular dimer and a dimeric pseudo-capsule. 1H and 19F NMR analyses …
Substituent Effects on the [N−I−N]+ Halogen Bond
2016
We have investigated the influence of electron density on the three-center [N–I–N]+ halogen bond. A series of [bis(pyridine)iodine]+ and [1,2-bis((pyridine-2-ylethynyl)benzene)iodine]+ BF4– complexes substituted with electron withdrawing and donating functionalities in the para-position of their pyridine nitrogen were synthesized and studied by spectroscopic and computational methods. The systematic change of electron density of the pyridine nitrogens upon alteration of the para-substituent (NO2, CF3, H, F, Me, OMe, NMe2) was confirmed by 15N NMR and by computation of the natural atomic population and the π electron population of the nitrogen atoms. Formation of the [N–I–N]+ halogen bond re…
Novel supramolecular affinity materials based on (−)-isosteviol as molecular templates
2013
The readily available ex-chiral-pool building block (−)-isosteviol was combined with the C3-symmetric platforms hexahydroxytriphenylene and hexaaminotriptycene providing large and rigid molecular architectures. Because of the persistent cavities these scaffolds are very potent supramolecular affinity materials for head space analysis by quartz crystal microbalances. The scaffolds serve in particular as templates for tracing air-borne arenes at low concentration. The affinities of the synthesized materials towards different air-borne arenes were determined by 200 MHz quartz crystal microbalances.
Self-assembly mechanism based on charge density topological interaction energies
2017
The packing interactions have been evaluated in the context of the self-assembly mechanism of crystal growth and also for its impacts on the aromaticity of the trimesate anion. The structure of ethylammonium trimesate hydrate (1) measured at 100 K and a charge density model, derived in part from theoretical structures, is reported. Theoretical structure factors were obtained from the geometry-optimized periodic wave function. The trimesic acid portion of 1 is fully deprotonated and participates in a variety hydrogen bonding motifs. Topological analysis of the charge density model reveals the most significant packing interactions and is then compared to a complementary analysis performed by …
The effect of the cation p-surface area on the 3D organization and catalytic ability of imidazolium-based ionic liquids
2011
The dichotomic nature of ionic liquids (ILs, simple solvents or supramolecular fluids) induced us to carry out a structural investigation of some mono-and dicationic ionic liquids using 1D and 2D NMR, resonance light scattering, and UV/Vis spectroscopy. Ionic liquids with different cation π-surface areas were used, namely [bmim][NTf2], [Bzmim][NTf 2], [Bzbim][NTf2], [p-Xyl-(bim)2][NTf 2]2, and [m-Xyl-(bim)2][NTf2] 2 [bmim = 1-butyl-3-methylimidazolium, Bzmim = 1-benzyl-3- methylimidazolium, Bzbim = 1-benzyl-3-butylimidazolium, NTf2 = bis(trifluoromethansulfonyl)imide]. In order to verify to what extent the structural investigation, coupled with the determination of solvent parameters, could…