scholarly journals NMR Studies into the Potential Interactions of Fullerene C60 with Tetraphenylporphyrin and Some of Its Derivatives

2010 ◽  
Vol 2010 ◽  
pp. 1-9
Author(s):  
C. Obondi ◽  
A. A. Rodriguez
Keyword(s):  
Stationary Phases ◽  
Nmr Relaxation ◽  
Interaction Process ◽  
Relaxation Rates ◽  
Electronic Effects ◽  
Nmr Studies ◽  
Noticeable Effect ◽  
H Nmr ◽  
Electron Donating Groups ◽  
Potential Interactions

1H NMR relaxation studies were employed to investigate potential interactions between C60 and tetraphenylporphyrin, H2[TPP], and parasubstituted tetraphenylporphyrins, H2[(p-X)4TPP], where X = CN and OCH3 in solution. The substituted porphyrins provided a means by which to investigate the role that electronic effects play in the interaction process. A comparison of the relaxation rates, R1, and correlation times, τC, of the pyrrole and phenyl hydrogens in these complexes, without and with the presence of C60, revealed that the introduction of C60 into solution did not have a noticeable effect on R1 and τC of these protons in H2[TPP], indicating the absence of long-term intermolecular interaction at either of these two sites. A similar analysis of the two protons in the other two substituted tetraphenylporphyrin analogs revealed slower molecular dynamics indicating the presence of intermolecular interactions. Stronger interactions were observed in H2[(p-OCH3)4TPP] indicating that the electron-donating abilities of the -OCH3 group promote the interaction process. Our results indicate that it is very likely that enhanced selectivity in the chemical purifications of fullerenes and metallofullerenes can be achieved by employing tetraphenylporphyrin-silica stationary phases which have been modified with electron-donating groups.

NMR studies of hydrocarbons solubilized in aqueous micellar solutions

1991 ◽  
Vol 69 (5) ◽  
pp. 822-833 ◽  
Author(s):  
Roderick E. Wasylishen ◽  
Jan C. T. Kwak ◽  
Zhisheng Gao ◽  
Elisabeth Verpoorte ◽  
J. Bruce MacDonald ◽  
...  
Keyword(s):  
Alkyl Chain ◽  
Chemical Shifts ◽  
Nmr Relaxation ◽  
Spin Lattice Relaxation ◽  
Ionic Surfactant ◽  
Nmr Studies ◽  
Unsaturated Hydrocarbons ◽  
Saturated Hydrocarbons ◽  
Surfactant Micelle ◽  
H Nmr

Information concerning the solubilization of hydrocarbons in ionic surfactant micelles was obtained from 2H NMR relaxation, 1H NMR chemical shifts, and 1H NMR paramagnetic relaxation measurements. The rotational motion of deuterated hydrocarbons, which is related to the micellar microviscosity at the location of the hydrocarbons, was probed by 2H NMR relaxation. The relaxation data are interpreted using both the two-step and the single-step models, and the results are discussed in terms of the micellar microviscosity and the location of the hydrocarbons in micelles. The location of the hydrocarbons in micelles was further investigated by determining the aromatic ring current-induced 1H chemical shifts along the surfactant alkyl chain and by comparing the 1H spin-lattice relaxation enhancement of the hydrocarbons and the surfactant alkyl chain, induced by Mn2+ on the micellar surface. The hydrocarbons used include benzene, naphthalene, acenaphthalene, triphenylene, cyclohexane, cyclododecane, and tert-butylcyclohexane and the surfactants studied are hexadecyl-, tetradecyl-, and dodecyltrimethylammonium bromide; hexadecyl-, tetradecyl-, and dodecylpyridinium halide; and sodium dodecyl sulfate. The results indicate that the micellar microviscosity at the location of saturated hydrocarbons is approximately 5 cP for both the cationic and anionic micelles, whereas the micellar microviscosity at the location of unsaturated hydrocarbons is much higher. The unsaturated hydrocarbons are found to reside primarily near the surfactant headgroup in the cationic micelles, but are distributed evenly throughout the anionic SDS micelles. The saturated hydrocarbons appear to be located in the interior of the micelles. Key words: NMR, relaxation, solubilization, surfactant, micelle.

NM R T1-Analysis of Methyl Tunnelling in Molecular Crystals at Intermediate Barriers

1987 ◽  
Vol 42 (11) ◽  
pp. 1266-1274 ◽  
Author(s):  
H. Langen ◽  
A.-S. Montjoie ◽  
W. Müller-Warmuth ◽  
Hildegard Stiller
Keyword(s):  
Low Temperatures ◽  
Fourier Expansion ◽  
Elevated Temperatures ◽  
Molecular Crystals ◽  
Nmr Relaxation ◽  
Methyl Isocyanate ◽  
Relaxation Rates ◽  
Potential Barriers ◽  
H Nmr ◽  
Temperature Dependences

The frequency and temperature dependences of the 1H NMR relaxation rates T1-1for rotating CH3 groups in solids look quite anomalous at intermediate hindering potential barriers. In order to explain the experimental behaviour and to extract parameters from the NMR T1 experiments that account for tunnelling at low temperatures and random reorientation at elevated temperatures, we have calculated T1-1vs. T-1 curves to be expected under various conditions. New experimental results for methyl iodide, methyl bromide, 3-methylthiophene, p-xylene, and methyl isocyanate have been fitted by this procedure and all the parameters that describe the motional behaviour have been derived. The single particle rotational potential has been determined using the first two terms of the Fourier expansion.

Proton NMR relaxation from molecular dynamics: intramolecular and intermolecular contributions in water and acetonitrile

2019 ◽  
Vol 21 (48) ◽  
pp. 26621-26629 ◽  
Author(s):  
Adam Philips ◽  
Jochen Autschbach
Keyword(s):  
Molecular Dynamics ◽  
Force Field ◽  
Ab Initio ◽  
Pure Water ◽  
Proton Nmr ◽  
Nmr Relaxation ◽  
Spin Rotation ◽  
Relaxation Rates ◽  
H Nmr

Accurate 1H NMR relaxation rates for protons in pure water and acetonitrile are computed via ab initio and force field molecular dynamics. Dipole–dipole and spin-rotation mechanisms are considered.

Predominant effect of connecting atom and position of substituents on azomethine nitrogens’ basicity in phthalocyanines

2016 ◽  
Vol 20 (08n11) ◽  
pp. 1122-1133 ◽  
Author(s):  
Antonin Cidlina ◽  
Jan Svec ◽  
Lucie Ludvová ◽  
Jiří Kuneš ◽  
Petr Zimcik ◽  
...  
Keyword(s):  
Weak Interactions ◽  
Equilibrium Constants ◽  
Van Der Waals Interactions ◽  
Azomethine Nitrogen ◽  
Electronic Effects ◽  
Nmr Studies ◽  
H Nmr ◽  
Significant Difference ◽  
Electronic Effects Of Substituents ◽  
Predominant Effect

The basicity of azomethine nitrogens was studied on a series of phthalocyanines (Pcs) that differed in a position of substituent, [Formula: see text] peripherally ([Formula: see text]-series) and non-peripherally substituted Pcs ([Formula: see text]-series), and in a type of substituent (alkylsulfanyl, alkyloxy or alkyl). Appropriate 3,6- or 4,5-disubstituted phthalonitriles were prepared either by nucleophilic substitution or by Negishi coupling. Target zinc Pcs were synthesized by Linstead method. The basicity was studied by the mean of absorption and1H NMR spectroscopies in chloroform upon titration with trifluoroacetic acid. Equilibrium constants (log [Formula: see text]) indicated significant difference within the series. Basicity decreased as follows: [Formula: see text]-alkyloxy ≫ [Formula: see text]-alkylsulfanyl > [Formula: see text]-alkyloxy > [Formula: see text]-alkyl > [Formula: see text]-alkylsulfanyl ∼ [Formula: see text]-alkyl with log [Formula: see text] higher than 7 down to 2.6 M[Formula: see text]. Increased basicity of [Formula: see text]-alkyloxy and [Formula: see text]-alkylsulfanyl Pcs is caused by the stabilization of trapped hydrogen at azomethine nitrogen via hydrogen bonding and van der Waals interactions, respectively. The basicity of [Formula: see text]-series clearly correlated with the electronic effects of substituents.1H NMR studies confirmed the possibility of the weak bonding interactions in [Formula: see text]-alkyloxy and [Formula: see text]-alkylsulfanyl Pcs, however, the position of the1H NMR signal of azomethine-NH proton was even more influenced by the electronic effects of present substituents than by the weak interactions.

Structure and Dynamics of Spherical and Rodlike Alkyl Ethoxylate Surfactant Micelles Investigated Using NMR Relaxation and Atomistic Molecular Dynamics Simulations

2019 ◽  
Author(s):  
Allison Edwards ◽  
Abdolreza Javidialesaadi ◽  
Katie Weigandt ◽  
George Stan ◽  
Charles Eads
Keyword(s):  
Molecular Dynamics ◽  
Molecular Dynamics Simulations ◽  
Nmr Relaxation ◽  
Cross Relaxation ◽  
Relaxation Rates ◽  
Surfactant Micelles ◽  
Cylindrical Micelles ◽  
Spherical Micelles ◽  
Dynamics Simulations ◽  
Relative Motions

We study molecular arrangements and dynamics in alkyl ethoxylate nonionic surfactant micelles by combining high field (600 and 700 MHz) NMR relaxation measurements with large-scale atomistic molecular dynamics simulations. For spherical micelles, but not for cylindrical micelles, cross relaxation rates are positive only for surfactant alkyl tail atoms connected to the hydrophilic head group. All cross relaxation rates are negative for cylindrical micelles. This effect is reproducible either by changing composition (ratios of the nonionic surfactants) or changing temperature of a single surfactant in order to change the micelle shape. We validate the micelle shape by SANS and use the results as a guide for our simulations. We calculate parameters that determine relaxation rates directly from simulated trajectories, without introducing specific functional forms. Results indicate that relative motions of nearby atoms are liquid-like, in agreement with 13C T1 measurements, though constrained by micelle morphology. Relative motions of distant atoms have slower components because the relative changes in distances and angles are smaller when the moving atoms are further apart. The slow, long-range motions appear to be responsible for the predominantly negative cross relaxation rates observed in NOESY spectra. The densities of atoms from positions 1 and 2 in the boundary region are lower in spherical micelles compared to cylindrical micelles. Correspondingly, motions in this region are less constrained by micelle morphology in the spherical compared to the cylindrical cases. The two effects of morphology lead to the unusual occurrence of positive cross relaxation involving positions 1 and 2 for spheres.

1H NMR Conformational Studies in Water of Angiotensin II Analogues Modified at the N- and C-Termini: Interactions of the Aromatic Side Chains and Folding of the N-Terminal Domain

1994 ◽  
Vol 59 (11) ◽  
pp. 2523-2532 ◽  
Author(s):  
John Hondrelis ◽  
John Matsoukas ◽  
George Agelis ◽  
Paul Cordopatis ◽  
Ning Zhou ◽  
...  
Keyword(s):  
Shielding Effect ◽  
Resonance Spectroscopy ◽  
Nmr Studies ◽  
Previous Suggestion ◽  
Aminoisobutyric Acid ◽  
H Nmr ◽  
Neutral Ph ◽  
Angiotensin Ii Analogues ◽  
Proton Resonances ◽  
Cosy Nmr

The conformation of [Sar1]angiotensin II in water at neutral pH has been examined by proton magnetic resonance spectroscopy at 400 MHz and in particular by comparing its 1H NMR spectral data with those of analogues modified at positions 1,4 and 6, namely [Sar1,Cha8]ANGII, [Des Asp1,Cha8]ANGII, [Aib1,Tyr(Me)4]ANGII, [Aib1,Tyr(Me)4,Ile8]ANGII, [N-MeAib1,Tyr(Me)4]ANGII, [N-MeAib1,Tyr(Me)4,Ile8]ANGII, ANGIII and [Sar1,Ile8]ANGII. Assignment of all proton resonances in these analogues was made possible by 2D COSY NMR experiments. The H-2 and H-4 protons for the histidine ring in [Sar1]ANGII, ANGII and ANGIII were shielded compared with the same protons in [Sar1,Ile8]ANGII, [Sar1,Cha8]ANGII and [Des Asp1,Cha8]ANGII; this shielding effect was not disturbed upon methylation of the tyrosine hydroxyl and/or replacement of residue 1 (sarcosine or aspartic acid) with aminoisobutyric acid (Aib) or N-methyl aminoisobutyric acid (N-MeAib). These data are consistent with our previous suggestion based on NMR studies in neutral DMSO that a characteristic folded conformation for ANGII previously observed in non-polar solvents can also be detected in water at neutral pH, but to a lesser degree.

High field 1H NMR Studies of Sol-Gel Kinetics

1986 ◽  
Vol 73 ◽  
Author(s):  
Bruce D. Kay ◽  
Roger A. Assink
Keyword(s):  
Equilibrium Distribution ◽  
Sol Gel ◽  
Nmr Studies ◽  
H Nmr ◽  
Rate Limiting Step ◽  
Rate Of Hydrolysis ◽  
Acid Catalyzed ◽  
Product Species ◽  
Rate Limiting ◽  
Kinetics Of

ABSTRACTHigh resolution 1H NMR spectroscopy at high magnetic fields is employed to study the reaction kinetics of the Si(OCH3)4:CH3OH:H2O sol-gel system. Both the overall extent of reaction as a function of time and the equilibrium distribution of species are measured. In acid catalyzed solution, condensation is the rate limiting step while in base catalyzed solution, hydrolysis becomes rate limiting. A kinetic model in which the rate of hydrolysis is assumed to be independent of the adjacent functional groups is presented. This model correctly predicts the distribution of product species during the initial stages of the sol-gel reaction.

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