Relaxation reagents specific

Using single-frequency and noise-modulated resonance and off-resonance proton decoupling, 7] relaxation time measurements, relaxation reagents like Gd (fod)3 and specifically deuterated compounds, all the carbons in retinal isomers, the model compounds a-and /i-ionone, and vitamin A and its isomers [165, 555-557] were assigned. The olefinic ring carbons (C-5 and C-6) could be identified on the assumption that the 13C relaxation times are dominated by intramolecular dipole-dipole interactions with neighboring protons and that the same rotational correlation time characterizes the interactions for both carbons. Consequently the ratio of T/s for C-5 and C-6 can be estimated from eq. (5.1)... 

The application of LSR to amino-acids has received some attention. (451-456, 498) Such studies are an essential preliminary to the use of LSR for amino-acid sequence determination in simple peptides and proteins. The latter are discussed more comprehensively in Section G. A detailed study has been made (453) of the interaction of Eu(iii), Pr(iii), Gd(iii), and La(iii) with iV-acetyl-L-3-nitrotyrosine in order to characterize the nitrotyrosine residue as a potential specific lanthanide binding site in proteins. The parameters of the dipolar interaction indicate a significant contribution from non axially symmetric terms. The conformations of the nucleotides cyclic j8-adenosine 3, 5 -phosphate (3, 5 -AMP) (457, 458) and adenosine triphosphate (ATP) (459) have been deduced using LSR. In the former case the conformation of the ribose and phosphate groups is consistent with the solid state structure. A combination of lanthanide shift and relaxation reagents was used to deduce the most favoured family of conformations for ATP in aqueous solution. One of these conformations corresponds closely to one of the crystal structure forms. 

Paramagnetic relaxation reagents capable of specifically interacting with a basic site of the investigated substrate can also be... 

Most biochemically relevant high-spin systems have such short 7j-relaxation times that their EPR is broadened beyond detection at ambient temperatures. An exception is the class of S = 5/2 Mn" systems with D hx. Also, S = 7/2 Gd"1-based MRI shift reagents exhibit readily detectable room-temperature EPR spectra. Otherwise, aqueous-solution transition ion bioEPR is limited to complexes of S = 1/2 metals, in particular Cu", and to a lesser extent VIV02+, NiIn, Ni1, Mov, and Wv. Cupric is the stable oxidation state of biological copper under aerobic conditions, however, the other metals are stable as Vv, Ni", MoVI, and WVI, and, therefore, the other oxidation states associated with S = 1/2 paramagnetism may exhibit oxidative or reductive reactivity and may thus require specific experimental precautions such as strict anaerobicity over the course of the EPR experiment. 

However, the spatial inhomogeneity in the distribution of reagents is not the only reason why the radiolysis of substances in the condensed state is different from that of gases. As we have already mentioned in Section VIII, as we pass from the gaseous state to the condensed one, at the primary stage of radiolysis we already observe a redistribution of yields of primary active particles (resulting in the increase of the yield of ionized states). Also different are the subsequent relaxation processes, as well as the processes of decay of excited and ionized states.354 Another specific feature of processes in a condensed medium is the cage effect, which slows down the decay of a molecule into radicals.355 Finally, the formation of solvated electrons is also a characteristic feature of radiation-chemical processes in liquids.356... 

The possibility of exploiting enhanced paramagnetic relaxation as an effective source of structural constraints was explored by JarOTiiec and coworkers on microcrystalline samples of a model protein, the B1 immunoglobulin-binding domain of protein G (GBl). Here a solvent-exposed cysteine residue was used to incorporate a thiol-specific paramagnetic nitroxide (TEMPO) or a thiol-specific EDTA-metal reagent bound to Cu and Mn° ions [99-101]. 

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