Dipolar intermolecular

Outer sphere relaxation arises from the dipolar intermolecular interaction between the water proton nuclear spins and the gadolinium electron spin whose fluctuations are governed by random translational motion of the molecules (106). The outer sphere relaxation rate depends on several parameters, such as the closest approach of the solvent water protons and the Gdm complex, their relative diffusion coefficient, and the electron spin relaxation rate (107-109). Freed and others (110-112) developed an analytical expression for the outer sphere longitudinal relaxation rate, (l/Ti)os, for the simplest case of a force-free model. The force-free model is only a rough approximation for the interaction of outer sphere water molecules with Gdm complexes. 

The relaxivity induced by gadolinium chelates due to inner-sphere water molecules, riIS, is well understood on the microscopic scale as can be seen from the above discussion. The contribution to the overall relaxation enhancement due to all other water molecules is normally summed up in the term r, generally called the outer-sphere contribution. The interaction between the water proton nuclear spin I and the gadolinium electron spin S is supposed to be a dipolar intermolecular interaction whose fluctuations are governed by random translational motion. The corresponding relaxation rate, l/Tly for unlike spins is given by Eq. (23) [88-90]... 

Dipolar substances with a strongly positive effect in solution in a non-dipolar liquid presenting a weak positive effect (e.g. nitrobenzene-benzene ) or in a dipolar liquid presenting a weak negative effect (e.g. 1,1-dichloroethane-nitrobenzene " ). Die inversion is due to dipolar intermolecular interactions. ... 

Poly(vinyl chloride) 80 Strong dipolar intermolecular forces... 

Gao Q, Scheinbeim JI, Newman BA (2000) Dipolar intermolecular interactions, structural development, and electromechanical properties in ferroelectric polymer blends of nylon-11 and poly(vinylidene fluoride). Macromolecules 33 7564... 

According to Hansen s theory [13], 5, the Hildebrand parameter, can be calculated using the three components 5, which represents the energy from dispersion bonds 5i which represents the energy from hydrogen bonds between molecules and 8p, which represents the energy from dipolar intermolecular forces ... 

Zwitterionic L-alanine ( HjN—CfCHj)—CO2—) is a dipolar molecule that forms large well-ordered crystals in which the molecules form hydrogen-bonded columns. The strong interactions lead to the presence of well-defined intra- and intermolecular vibrations that can usefully be described using hannonic theory. 

MF < MC1 < MBr < MI . By contrast for less-ionic halides with significant non-coulombic lattice forces (e.g. Ag) solubility in water follows the reverse sequence MI < MBr < MC1 < MF . For molecular halides solubility is determined principally by weak intermolecular van der Waals and dipolar forces, and dissolution is commonly favoured by less-polar solvents such as benzene, CCI4 or CS2. 

The rhodium-catalyzed tandem carbonyl ylide formation/l,3-dipolar cycloaddition is an exciting new area that has evolved during the past 3 years and high se-lectivities of >90% ee was obtained for both intra- and intermolecular reactions with low loadings of the chiral catalyst. 

Intramolecular and intermolecular 1,3-dipolar cycloadditions of aziridine-2-car-boxylic esters with alkenes and alkynes have been investigated [131, 132]. Upon heating, aziridine-2-carboxylates undergo C-2-C-3 bond cleavage to form azome-... 

A family of interesting polycychc systems 106 related to pyrrolidines was obtained in a one-pot double intermolecular 1,3-dipolar cycloaddition, irradiating derivatives of o-allyl-sahcylaldehydes with microwaves in toluene for 10 min in presence of the TEA salt of glycine esters [71]. A very similar approach was previously proposed by Bashiardes and co-workers to obtain a one-pot multicomponent synthesis of benzopyrano-pyrrolidines 107 and pyrrole products 108 (Scheme 37). The latter cycloadducts were obtained when o-propargylic benzaldehydes were utihzed instead of o-allyhc benzalde-hydes, followed by in situ oxidation [72]. 

In 8CB, continued cooling into the smectic phase reveals the appearance of a broad ultra-low-frequency feature centred at around 10 cm where no other modes are seen. This is shown in Fig. 15. This feature appears to be unique to the smectic phase and has been tentatively attributed to intermolecular dipolar coupling across smectic layers [79]. In principle this should be a generic feature of smectics but it will be necessary to explore this issue through extensive computer simulations using realistic, shape-dependent potentials for... 

Here, is the magnetization of spin i at thermal equilibrium, p,j is the direct, dipole-dipole relaxation between spins i and j, a-y is the crossrelaxation between spins i and j, and pf is the direct relaxation of spin i due to other relaxation mechanisms, including intermolecular dipolar interactions and paramagnetic relaxation by dissolved oxygen. Under experimental conditions so chosen that dipolar interactions constitute the dominant relaxation-mechanism, and intermolecular interactions have been minimized by sufficient dilution and degassing of the sample, the quantity pf in Eq. 3b becomes much smaller than the direct, intramolecular, dipolar interactions, that is. 

The dispersion forces in acetone are nearly the same as those in 2-methylpropane, but the addition of dipolar forces makes the total amount of intermolecular attraction between acetone molecules substantially greater than the attraction between molecules of 2-methylpropane. Consequently, acetone boils at a considerably higher... 

Methyl ethyl ether is a gas at room temperature (boiling point = 8 °C), but 1-propanol, shown in Figure 11-13. is a liquid (boiling point = 97 °C). The compounds have the same molecular formula, C3 Hg O, and each has a chain of four inner atoms, C—O—C—C and O—C—C—C. Consequently, the electron clouds of these two molecules are about the same size, and their dispersion forces are comparable. Each molecule has an s p -hybridized oxygen atom with two polar single bonds, so their dipolar forces should be similar. The very different boiling points of 1-propanol and methyl ethyl ether make it clear that dispersion and dipolar forces do not reveal the entire story of intermolecular attractions. 

Cross-relaxation The mutual intermolecular or intramolecular relaxation of magnetically equivalent nuclei, e.g., through dipolar relaxation. This forms the basis of nOe experiments. 

SEC analysis shows that some samples have a blmodal MWD. At this time it is not possible to tell whether the bimodallty is an artifact of the polymerization mechanism or, perhaps, a consequence of partial hydrolysis of the polymer i.e., the high MW shoulder in Figure 5 may be due to the formation of aggregates through Intermolecular dipolar interactions of P-OH side groups or to polymer molecules crosslinked by P-O-P bonds. 

Compounds in which a carbonyl or other nucleophilic functional group is close to a carbenoid carbon can react to give ylide intermediate.221 One example is the formation of carbonyl ylides that go on to react by 1,3-dipolar addition. Both intramolecular and intermolecular cycloadditions have been observed. 

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