0000000000054905
AUTHOR
David ŠAman
Polyamine conjugates of stigmasterol.
Abstract Three new polyamine conjugates with stigmasterol [(3β,22 E )-stigmasta-5,22-dien-3-ol] were synthesized and subjected to basic antimicrobial and cytotoxic tests. The conjugate derived from spermine, (3β,22 E )-stigmasta-5,22-dien-3-yl 4(12-amino-4,9-diaza-dodecylamino)-4-oxobutanoate ( 5c ), displayed considerable antimicrobial activity on Staphylococcus aureus at low concentration (50 μg mL −1 ). The cytotoxic activity was tested on cells of human T-lymfoblastic leukemia (IC 50 = 35.8 ± 10.3 μM ( 5c ) and IC 50 = 35.9 ± 5.7 μM ( 5b )) and normal human fibroblasts (IC 50 = 38.0 ± 2.8 μM ( 5c ) and IC 50 = 45.5 ± 1.9 μM ( 5b )). Conjugate 5a displayed no activity in both tests.
13C and15N NMR study of substituted 1,2,4-triazines
13C and 15N NMR spectra of eight substituted 1,2,4-triazines were measured and assigned. The assignments of the 13C NMR spectra were based on the substituent chemical shifts and nJ(C,H) coupling constants. 15N NMR chemical shifts generally showing well separated ranges were assigned by the proton coupled 15N NMR spectra. 15N NMR chemical shifts of N-4 in 3- and 5-methoxy or -thiomethyl-substituted 1,2,4-triazines were found to be related significantly (confidence level >99%) with the π-charge at N-4 calculated by a semi-empirical molecular orbital (AM1) procedure. For the 15N NMR chemical shifts of N-1 and N-2, no reliable correlations with the molecular electronic properties such as AM1 π-…
Spectral and microscopic study of self-assembly of novel cationic spermine amides of betulinic acid
Supramolecular characteristics of two spermine amides of betulinic acid (1 and 2) were studied by measuring and evaluating their UV-VIS-NIR spectra in aqueous acetonitrile and DOSY-NMR spectra in tetradeuteromethanol, accompanied by atomic force microscopy (AFM) images, scanning electron microscopy (SEM) micrographs, and transmission electron microscopy (TEM) micrographs. Fibrous supramolecular self-assembly of 1 and 2 was observed by AFM images, as well as by the SEM and TEM micrographs. Bathochromic shifts of the absorbance maximum at 870nm to 1015-970nm in the UV-VIS-NIR spectra were observed with increasing water content in the acetonitrile/water systems, indicating formation of fibrous…
13C and15N NMR chemical shift assignments ofN-1-(2- azidoethyl)-4-R-pyrimidin-2-ones by1H,X HMQ(B)C withz-gradient selection
13C and 15N NMR chemical shift assignments based on z-gradient selected 1H,X (X=13C and 15N) HMQC and HMBC experiments are reported for N-1-(2-azidoethyl)pyrimidin-2-one (ring system of cytosine), its five 4-R derivatives [where R=NH2, OCH3, N(CH2)4, NHCH2CH(CH3)2 and N(CH3)2] and 2-azidoethyl tosylate. The possibilities of detecting all nitrogens in these molecules containing (i) an azido group at N-1 and (ii) an electronegative substituent at C-4 are limited. First, the terminal nitrogen of the azido group is difficult to observe because the nearest proton (in a CH2 group) is located four bonds away from it. Second, in contrast to N-1, N-3 in N-1-(2-azido-ethyl)-4-pyrimidin-2-ones remaine…
Rapid Self-Healing and Thixotropic Organogelation of Amphiphilic Oleanolic Acid–Spermine Conjugates
Natural and abundant plant triterpenoids are attractive starting materials for the synthesis of conformationally rigid and chiral building blocks for functional soft materials. Here, we report the rational design of three oleanolic acid-triazole-spermine conjugates, containing either one or two spermine units in the target molecules, using the Cu(I)-catalyzed Huisgen 1,3-dipolar cycloaddition reaction. The resulting amphiphile-like molecules 2 and 3, bearing just one spermine unit in the respective molecules, self-assemble into highly entangled fibrous networks leading to gelation at a concentration as low as 0.5% in alcoholic solvents. Using step-strain rheological measurements, we show ra…
Rapid Self-Healing and Thixotropic Organogelation of Amphiphilic Oleanolic Acid–Spermine Conjugates
Natural and abundant plant triterpenoids are attractive starting materials for the synthesis of conformationally rigid and chiral building blocks for functional soft materials. Here, we report the rational design of three oleanolic acid–triazole–spermine conjugates, containing either one or two spermine units in the target molecules, using the Cu(I)-catalyzed Huisgen 1,3-dipolar cycloaddition reaction. The resulting amphiphile-like molecules 2 and 3, bearing just one spermine unit in the respective molecules, self-assemble into highly entangled fibrous networks leading to gelation at a concentration as low as 0.5% in alcoholic solvents. Using step-strain rheological measurements, we show ra…
Studies on supramolecular gel formation using DOSY NMR
Herein, we present the results obtained from our studies on supramolecular self-assembly and molecular mobility of low-molecular-weight gelators (LMWGs) in organic solvents using pulsed field gradient (PFG) diffusion ordered spectroscopy (DOSY) NMR. A series of concentration-dependent DOSY NMR experiments were performed on selected LMWGs to determine the critical gelation concentration (CGC) as well as to understand the behaviour of the gelator molecules in the gel state. In addition, variable-temperature DOSY NMR experiments were performed to determine the gel-to-sol transition. The PFG NMR experiments performed as a function of gradient strength were further analyzed using monoexponential…
Glycosidic juvenogens: derivatives bearing alpha,beta-unsaturated ester functionalities.
Abstract A series of the protected alkyl glycosides 5a / 5b – 12a / 12b was synthesized from the parent isomeric alcohols (insect juvenile hormone bioanalogs; juvenoids), 4-[4′-(2″-hydroxycyclohexyl)methylphenoxy]-3-methyl-but-2-enoic acid ethyl ester ( 1a / 1b – 4a / 4b ; racemic structures) and ( 1a – 4a ; enantiopure structures). Cadmium carbonate was used as a promoter of this Koenigs–Knorr reaction, and the products were obtained in 82–92% yields. Deprotection of the carbohydrate functionality of 5a / 5b – 12a / 12b was carefully performed using ethanolysis in the presence of zinc acetate, due to the presence of another ester functionality in the aglycone part of the molecule of protec…