Search results for " effect"
showing 10 items of 7524 documents
Experimental studies of the rheological behavior of a demixing biopolymeric sol
1995
Experimental data are presented concerning a large transient viscosity surge occurring in the course of spinodal demixing of agarose aqueous solutions. The study includes the effects of water perturbation by minor proportions of compatible cosolutes. Three observations are noteworthy. One concerns an upward or downward shift of the spinodal temperature, caused by cosolutes, which agrees with their expected modulation of solvent-induced forces. The second concerns the time of appearance of the viscosity surge. This is observed to follow a critical law, with an exponent independent of polymer concentration and solvent perturbation. The third concerns the inverse-power-law dependence of the vi…
B-DNA Structure and Stability as Function of Nucleic Acid Composition. Dispersion-Corrected DFT Study of Dinucleoside-Monophosphate Single and Double…
2013
actions of the sugar-phosphate skeleton with water; (6) hydrophobic interactions of the DNA cylindrical core, made up by the hydrogen-bonded and stacked nitrogen bases, with the water solvent. Recently, there has been increasing effort in developing and applying quantum chemical methods able to reproduce the structure of native B-DNA and to correctly describe the energy involved in the intrastrand and interstrand noncovalent interactions between the nucleotide monomers. This topic has been approached by both wave function methods and density functional theory. [2] Water solvent and sodium counterions also play an important role in the formation and relative stabilization of the double-helic…
1H,13C,17O and19F NMR spectroscopic study of isomeric ring-substituted monofluoro-(E)-3-phenylpropenals
1993
Isomeric ring substituted monofluoro-(E)-3-phenylpropenals (cinnamaldehydes) were synthesized in order to provide, with the NMR-active 19F nucleus, an insight into the influence of substituents and the transmission of electronic effects between the aromatic ring and the side-chain. Their 1H, 13C and 17O NMR chemical shifts and their nJ(H,H), nJ(H,F), nJ(C,H) and nJ(C,F) values were determined. Generally, the nJ(C,F) coupling constants correlate with the length of the coupling route and thus simplify the assignments of the 13C NMR spectra. Only the side-chain carbons C-2 and C-3 in the ortho-substituted compounds showed an exception to this rule. Many long-range nJ(H,F) (n = 4–7) values were…
ChemInform Abstract: Conjugated Compounds Based on Vinylthiazole Units.
2008
Conjugated oligomers attract increasing attention because of their interesting properties in materials science [1]. Moreover, they are model compounds for conjugated polymers. Molecules polarized by electronic effects, in particular push-pull systems having terminal donor-acceptor substitution represent a special class of such oligomers [2]. Their major applications are in the field of nonlinear optics (NLO), twophoton absorption (TPA), two-photon induced fluorescence (TPIF), and photorefractive materials (PR). Fig. 1 illustrates known 2,5-thienylenevinylenes with zwitterionic resonance structures 1 (D = NR2; A = NO2, CHO, SO2R; n = 1, 2) [3, 4]. The corresponding compounds 2 with thiazole …
Internal rotation of 1,2-dichloroethane in haloalkane dehalogenase. A test case for analyzing electrostatic effects in enzymes
2003
1,2-Dichoroethane (DCE) is a prototypical molecule for studying electrostatic solvent effects on molecular conformation as far as rotation around the carbon−carbon bond notably changes the electric...
Substituent effects on axle binding in amide pseudorotaxanes: comparison of NMR titration and ITC data with DFT calculations
2012
The binding behaviour of differently substituted diamide axle molecules to Hunter/Vögtle tetralactam macrocycles was studied with a combination of NMR titration, isothermal titration calorimetry (ITC) experiments and calculations employing density functional theory (DFT), along with dispersion-corrected exchange-correlation functionals. Guests with alkyl or alkenyl chains attached to the diamide carbonyl groups have a significantly higher binding affinity to the macrocycle than guests with benzoyl amides and their substituted analogues. While the binding of the benzoyl and alkenyl substituted axles is enthalpically driven, the alkyl-substituted guest binds mainly because of a positive bindi…
Cation-π interactions between neutral calix[5]arene hosts and cationic organic guests
1997
Abstract The binding properties of the 1,3-bridged calix[5]crowns 1–3 towards a number of quaternary ammonium, phosphonium, and iminium ions have been investigated by 1H NMR in CDCl3 solution, where the sole driving force for association is provided by cation-π interactions. We have found that the cavity of a calix[5]arene fixed in a cone-like conformation provides a fairly efficient, but rather unselective, receptor site for quaternary salts. The conformationally mobile p-tert-butylcalix[5]arene (4) is in general a much less efficient binder than the more preorganized calixcrowns, but displays a remarkable selectivity towards N-methylquinuclidinium ion that is believed to arise from a good…
Asymmetrically substituted calix[4]arenes; A two-dimensional 1H NMR study of a tetraester derivative in the cone-conformation
1991
Abstract Several new chiral calix[4]arenes with three or four different substituents in the p-position have been prepared by fragment condensation. Standard derivatization procedures always led to the formation of mixtures of various conformational isomers from which the derivative in the cone-conformation could be isolated only by preparative HPLC. For a tetraester derivative it was shown by two-dimensional 1H NMR spectroscopy, that due to the different substituents the cone-conformation is strongly distorted. The sodium complex of this tetraester, however, assumes a regular cone-conformation again.
On the use of multi-parameter free energy relationships: the rearrangement of (Z)-arylhydrazones of 5-amino-3-benzoyl-1,2,4-oxadiazole into (2-aryl-5…
2010
Abstract By using a multi-parameter approach (a combination of Hammett/Ingold-Yukawa-Tsuno/Fujita-Nishioka free energy relationships) the mononuclear rearrangements of heterocycles (MRH) rates for five new ortho-substituted and ten new di-, tri-, or tetra-substituted (Z)-arylhydrazones of 5-amino-3-benzoyl-1,2,4-oxadiazole into the relevant (2-aryl-5-phenyl-2H-1,2,3-triazol-4-yl)ureas (in dioxane/water and in a large range of pS+ values) have been related to the electronic and proximity effects exerted by the present substituents, also considering previous results on some mono meta- and para-substituted (Z)-arylhydrazones. In every case, excellent correlation coefficients have been calculat…
Impact of Molecular Size and Shape on the Supramolecular Co‐Assembly of Chiral Tricarboxamides: A Comparative Study
2020
We report herein a comparative investigation of the chiral amplification features of a series of three families of C 3 -symmetric tricarboxamides: 1,3,5-triphenylbenzenetricarboxamides (TPBAs), benzenetricarboxamides (BTAs) and oligo(phenylene ethynylene) tricarboxamides (OPE-TAs). As previously observed for BTAs and OPE-TAs, a similar dichroic response is obtained for TPBAs decorated with three, two or only one chiral side chain bearing stereogenic centers, thus confirming the efficient transfer of point chirality to the supramolecular helical aggregates. Unlike BTAs and OPE-TAs, the chiral amplification ability of TPBAs in majority rules experiments shows a negligible dependence on the nu…