Influence of odd–even effect and intermolecular interactions in 2D molecular layers of bisamide organogelators

Kocasoy, Volga; Dedeoglu, Burcu; Demir-Ordu, Öznur; Avi̇yente, Vi̇ktorya

doi:10.1039/c8ra06224b

Cited by 7 publications

(6 citation statements)

References 39 publications

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“…Regarding the effect of the methylene linker length, in the amide series the activity seems to increase with the number of carbon atoms of the linker (see, for example, the activities of compounds 5a – 5c and 7a – 7c ) at least for ester derivatives, whereas for the corresponding acids the effect is less evident ( 6a vs 6b ) or opposite ( 6c vs 6d ). On the other hand, an “odd/even effect” − seems to occur in the urea series, where an even number of carbon atoms in the alkyl spacer (as in the case of 7b and 7e , n = 2, total carbon atoms in the linker = 4) is less favorable than an odd number (as in the case of 7a and 7d  n = 1, total carbon atoms in the linker = 3or 7c  n = 3, total carbon atoms in the linker = 5).…”

Section: Resultsmentioning

confidence: 99%

Turning Nonselective Inhibitors of Type I Protein Arginine Methyltransferases into Potent and Selective Inhibitors of Protein Arginine Methyltransferase 4 through a Deconstruction–Reconstruction and Fragment-Growing Approach

et al. 2022

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Protein arginine methyltransferases (PRMTs) are important therapeutic targets, playing a crucial role in the regulation of many cellular processes and being linked to many diseases. Yet, there is still much to be understood regarding their functions and the biological pathways in which they are involved, as well as on the structural requirements that could drive the development of selective modulators of PRMT activity. Here we report a deconstruction–reconstruction approach that, starting from a series of type I PRMT inhibitors previously identified by us, allowed for the identification of potent and selective inhibitors of PRMT4, which regardless of the low cell permeability show an evident reduction of arginine methylation levels in MCF7 cells and a marked reduction of proliferation. We also report crystal structures with various PRMTs supporting the observed specificity and selectivity.

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Section: Resultsmentioning

confidence: 99%

Turning Nonselective Inhibitors of Type I Protein Arginine Methyltransferases into Potent and Selective Inhibitors of Protein Arginine Methyltransferase 4 through a Deconstruction–Reconstruction and Fragment-Growing Approach

et al. 2022

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“…Although polymer materials are commonly used as thickeners/gelators, they have significant disadvantages: their molecular weight is difficult to control, and once the polymer is dissolved, the viscosity of the gel does not decrease even at high temperatures, resulting in poor operability. In contrast to conventional polymer gels, supramolecular gels have attracted attention in recent years [ 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 ]. Supramolecular gels are formed by the self-assembly of low-molecular-weight gelators (LMWGs), which form fibrous aggregates and 3D network structures with them.…”

Section: Introductionmentioning

confidence: 99%

Amidoamine Oxide Surfactants as Low-Molecular-Weight Hydrogelators: Effect of Methylene Chain Length on Aggregate Structure and Rheological Behavior

Kakehashi

Tokai

Nakagawa

et al. 2023

Gels

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Rheology control is an important issue in many industrial products such as cosmetics and paints. Recently, low-molecular-weight compounds have attracted considerable attention as thickeners/gelators for various solvents; however, there is still a significant need for molecular design guidelines for industrial applications. Amidoamine oxides (AAOs), which are long-chain alkylamine oxides with three amide groups, are surfactants that act as hydrogelators. Here, we show the relationship between the length of methylene chains at four different locations of AAOs, the aggregate structure, the gelation temperature Tgel, and the viscoelasticity of the formed hydrogels. As seen from the results of electron microscopic observations, the aggregate structure (ribbon-like or rod-like) can be controlled by changing the length of methylene chain in the hydrophobic part, the length of methylene chain between the amide and amine oxide groups, and the lengths of methylene chains between amide groups. Furthermore, hydrogels consisting of rod-like aggregates showed significantly higher viscoelasticity than those consisting of ribbon-like aggregates. In other words, it was shown that the gel viscoelasticity could be controlled by changing the methylene chain lengths at four different locations of the AAO.

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“…By analogy, the different H-bonding patterns may cause specific self-assembly behavior for odd and even bisamides in the gel state. In fact, in the presence of appropriate organic solvents, this class of bisamide gelators can form gels with different morphologies and microstructural properties. , The gelation process and final morphology of a series of α,ω-polymethylene bisamides, with the two amide groups bridged by even or odd numbers of spacer carbons, has been studied in a variety of solvents . It was found that the odd–even effect has a determining role on the gelability and the final properties of the gels; the bisamide gelators with even spacer length have shown the ability to gelate mesitylene.…”

Section: Introductionmentioning

confidence: 99%

Molecular Arrangement and Thermal Properties of Bisamide Organogelators in the Solid State

et al. 2022

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The crystal structure and phase behavior of bisamide gelators are investigated using differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy, Xray diffraction (XRD), and molecular modeling, aiming at a better understanding of bisamide gel systems. A homologous series of bisamide model compounds (nBAs) were prepared with the (CH 2 ) n spacer between the two amide groups, where n varies from 5 to 10, and with two symmetric C17 alkyl tails. With increasing spacer length, the thermal properties show a clear odd−even effect, which was characterized using our newly developed analytical model DSC N (T). Using XRD, all studied nBA compounds turn out to have a layer-like structure. The XRD patterns of the odd BA series are very similar but show marked differences compared to the XRD patterns of the even series, which in turn are very similar. The odd-membered 5BA molecules are nearly perpendicular to the stacked layers, as described by a pseudo-orthorhombic unit cell, whereas the even-membered 6BA molecules are tilted at an angle with respect to the layer normal, as described by a triclinic unit cell. In both the odd and even series, the inter-layer interaction is the van der Waals interaction. The 6BA hydrogen bonding scheme is very similar to that of Nylon 6,10 α, unlike the 5BA H bonding scheme. The packing of the C17 alkyl tails in the 5BA layers is similar to polyethylene, and unlike 6BA. The slightly higher crystalline density of 6BA (1.038 g cm −3 ) as compared to 5BA (1.018 g cm −3 ) explains the higher melting point, higher enthalpy of fusion, and the observed shift of N−H stretch bands to higher wave numbers. The structural differences observed between the odd and even BA series reflect the different structure-directing effect of parallel versus antiparallel amide hydrogen bonding motifs. These differences underlie the observed odd−even effect in the thermal properties of nBA compounds.

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Influence of odd–even effect and intermolecular interactions in 2D molecular layers of bisamide organogelators

Abstract: Our computational results rationalize the factors that affect the molecular self-assembly of bisamides and its role on gelation.

Cited by 7 publications

References 39 publications

Turning Nonselective Inhibitors of Type I Protein Arginine Methyltransferases into Potent and Selective Inhibitors of Protein Arginine Methyltransferase 4 through a Deconstruction–Reconstruction and Fragment-Growing Approach

Turning Nonselective Inhibitors of Type I Protein Arginine Methyltransferases into Potent and Selective Inhibitors of Protein Arginine Methyltransferase 4 through a Deconstruction–Reconstruction and Fragment-Growing Approach

Amidoamine Oxide Surfactants as Low-Molecular-Weight Hydrogelators: Effect of Methylene Chain Length on Aggregate Structure and Rheological Behavior

Molecular Arrangement and Thermal Properties of Bisamide Organogelators in the Solid State

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